JP7423532B2 - Honeycomb structure, exhaust gas purification device, exhaust system, and manufacturing method of honeycomb structure - Google Patents

Honeycomb structure, exhaust gas purification device, exhaust system, and manufacturing method of honeycomb structure Download PDF

Info

Publication number
JP7423532B2
JP7423532B2 JP2020536318A JP2020536318A JP7423532B2 JP 7423532 B2 JP7423532 B2 JP 7423532B2 JP 2020536318 A JP2020536318 A JP 2020536318A JP 2020536318 A JP2020536318 A JP 2020536318A JP 7423532 B2 JP7423532 B2 JP 7423532B2
Authority
JP
Japan
Prior art keywords
honeycomb structure
surface layer
magnetic particles
structure according
manufacturing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
JP2020536318A
Other languages
Japanese (ja)
Other versions
JPWO2020031434A1 (en
Inventor
由紀夫 宮入
岳秀 下田
崇志 青木
浩文 坂本
昌明 桝田
厚男 近藤
有仁枝 泉
恭平 加藤
倫弘 脇田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGK Insulators Ltd
Original Assignee
NGK Insulators Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Publication of JPWO2020031434A1 publication Critical patent/JPWO2020031434A1/en
Application granted granted Critical
Publication of JP7423532B2 publication Critical patent/JP7423532B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2006Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating
    • F01N3/2013Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating using electric or magnetic heating means
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/022Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
    • F01N3/0222Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D39/00Filtering material for liquid or gaseous fluids
    • B01D39/14Other self-supporting filtering material ; Other filtering material
    • B01D39/20Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418Honeycomb filters
    • B01D46/2422Mounting of the body within a housing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418Honeycomb filters
    • B01D46/2425Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/2429Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material of the honeycomb walls or cells
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418Honeycomb filters
    • B01D46/2425Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/24491Porosity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418Honeycomb filters
    • B01D46/2425Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/24492Pore diameter
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418Honeycomb filters
    • B01D46/2425Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
    • B01D46/24494Thermal expansion coefficient, heat capacity or thermal conductivity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418Honeycomb filters
    • B01D46/2451Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
    • B01D46/2474Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure of the walls along the length of the honeycomb
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418Honeycomb filters
    • B01D46/2451Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
    • B01D46/2476Monolithic structures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/24Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
    • B01D46/2403Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
    • B01D46/2418Honeycomb filters
    • B01D46/2451Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
    • B01D46/2482Thickness, height, width, length or diameter
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/42Auxiliary equipment or operation thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/85Coating or impregnation with inorganic materials
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N1/00Silencing apparatus characterised by method of silencing
    • F01N1/003Silencing apparatus characterised by method of silencing by using dead chambers communicating with gas flow passages
    • F01N1/006Silencing apparatus characterised by method of silencing by using dead chambers communicating with gas flow passages comprising at least one perforated tube extending from inlet to outlet of the silencer
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/023Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
    • F01N3/027Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles using electric or magnetic heating means
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/0335Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with exhaust silencers in a single housing
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28Construction of catalytic reactors
    • F01N3/2803Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825Ceramics
    • F01N3/2828Ceramic multi-channel monoliths, e.g. honeycombs
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28Construction of catalytic reactors
    • F01N3/2839Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration
    • F01N3/2853Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration using mats or gaskets between catalyst body and housing
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28Construction of catalytic reactors
    • F01N3/2882Catalytic reactors combined or associated with other devices, e.g. exhaust silencers or other exhaust purification devices
    • F01N3/2885Catalytic reactors combined or associated with other devices, e.g. exhaust silencers or other exhaust purification devices with exhaust silencers in a single housing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/90Physical characteristics of catalysts
    • B01D2255/915Catalyst supported on particulate filters
    • B01D2255/9155Wall flow filters
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2230/00Combination of silencers and other devices
    • F01N2230/02Exhaust filters
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2230/00Combination of silencers and other devices
    • F01N2230/04Catalytic converters
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2330/00Structure of catalyst support or particle filter
    • F01N2330/06Ceramic, e.g. monoliths
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/10Internal combustion engine [ICE] based vehicles
    • Y02T10/12Improving ICE efficiencies

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Geometry (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Ceramic Engineering (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Thermal Sciences (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Processes For Solid Components From Exhaust (AREA)
  • Filtering Materials (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)

Description

本発明は、ハニカム構造体、排気ガス浄化装置、排気システム及びハニカム構造体の製造方法に関する。とりわけ、電気加熱によるカーボン微粒子などの燃焼除去が可能であるとともに、凝縮水が発生する位置でも使用可能であり、凝縮水やカーボン堆積による短絡の問題がなく、圧力損失も低いハニカム構造体、排気ガス浄化装置、排気システム及びハニカム構造体の製造方法に関する。 The present invention relates to a honeycomb structure, an exhaust gas purification device, an exhaust system, and a method for manufacturing a honeycomb structure. In particular, it is possible to burn and remove carbon particles by electric heating, and it can also be used in locations where condensed water is generated.There is no problem of short circuits due to condensed water or carbon deposits, and the honeycomb structure and exhaust gas have low pressure loss. The present invention relates to a gas purification device, an exhaust system, and a method for manufacturing a honeycomb structure.

自動車の排ガスには、通常は不完全燃焼の結果としてカーボンなどの微粒子が含まれる。人体への健康被害低減の観点から、自動車排ガス中の微粒子低減要求が高まっている。現在、自動車動力源の主流であるガソリンエンジンから排出される微粒子も限りなく0に近い排出への低減が要求される。また、ディーゼルエンジンの排ガス微粒子についても同様の要求がある。 Automobile exhaust gas usually contains particulates such as carbon as a result of incomplete combustion. From the perspective of reducing health damage to the human body, there is an increasing demand for reducing particulates in automobile exhaust gas. Currently, there is a need to reduce particulate emissions from gasoline engines, which are the main power source for automobiles, to as close to zero as possible. Similar requirements also apply to diesel engine exhaust gas particles.

このような要求に応えるために、特許文献1には、流体の流路となる複数のセルを区画形成する多孔質の隔壁と最外周に位置する外周壁とを有するハニカム構造部と、前記ハニカム構造部の、流体の入口側の端面における所定の前記セルの開口部及び流体の出口側の端面における残余の前記セルの開口部に配設された目封止部とを備えるハニカム構造体が提案されている。また、特許文献2には、ハニカムフィルタの隔壁の表面に表層を設けて、PM堆積時の圧力損失などの課題を解決する技術が提案されている。 In order to meet such demands, Patent Document 1 discloses a honeycomb structure having a porous partition wall defining a plurality of cells serving as fluid flow paths and an outer peripheral wall located at the outermost periphery; A honeycomb structure is proposed, which includes a plugging portion disposed in a predetermined cell opening on an end face on the fluid inlet side of the structure and a plugging portion disposed in the remaining cell openings on the fluid outlet side end face of the structure. has been done. Further, Patent Document 2 proposes a technique for solving problems such as pressure loss during PM deposition by providing a surface layer on the surface of the partition wall of a honeycomb filter.

そして、上記のフィルタを車両に搭載する際、搭載スペース確保の観点からは、比較的スペースの余裕のある床下位置に搭載することが、排気システム構成上の設計自由度確保の観点から好ましい。しかしながら、床下配置にすると、エンジンからの排ガス温度が低くなり、フィルタに溜まった微粒子(カーボン微粒子)の燃焼が進まず、カーボン微粒子が蓄積してしまい、圧損の過大な上昇を引き起こして、エンジンの出力低下を招く問題がある。これを回避するため、特許文献3に開示されているように、電流を導電性のハニカム構造体自体に流し、そのジュール熱でハニカム構造体自体を加熱する方法が提案されている。また、凝縮水が発生する環境でも使用可能であり、カーボン微粒子が堆積する条件でも使用可能な加熱技術として、特許文献4にはハニカム構造体自身に電流を流さず、非導電性ハニカムセルに金属ワイヤを挿入して、ハニカム構造体の外周面を周回するように構成されたコイルにより誘導加熱する方法が開示されている。 When mounting the above-mentioned filter on a vehicle, from the viewpoint of securing mounting space, it is preferable to mount it under the floor where there is relatively sufficient space, from the viewpoint of securing design freedom in the configuration of the exhaust system. However, when placed under the floor, the temperature of the exhaust gas from the engine becomes low, and the combustion of particulates (carbon particulates) accumulated in the filter does not progress, causing carbon particulates to accumulate, causing an excessive increase in pressure drop, and causing engine damage. There is a problem that causes a decrease in output. In order to avoid this, a method has been proposed, as disclosed in Patent Document 3, in which a current is passed through the conductive honeycomb structure itself and the honeycomb structure itself is heated with the Joule heat. In addition, as a heating technology that can be used in environments where condensed water is generated and where carbon particles are deposited, Patent Document 4 describes a heating technology that can be used in environments where condensed water is generated and where carbon particles are deposited. A method is disclosed in which a wire is inserted and induction heating is performed using a coil configured to circulate around the outer peripheral surface of a honeycomb structure.

特許第4920752号公報Patent No. 4920752 特許第5616059号公報Patent No. 5616059 特許第5261256号公報Patent No. 5261256 米国特許公開第2017/0022868号US Patent Publication No. 2017/0022868

本発明者らの検討の結果、特許文献3に開示された技術では、ハニカム構造体に電気を通すため、排ガス中に凝縮水が排気管内で生成されると、電気短絡が発生してしまう問題があることが分かった。また、カーボン微粒子の堆積により電気的に短絡してしまう問題もあることが分かった。
また、特許文献4に開示された技術をハニカム構造フィルタに適用すると、一部のセルがガス流路として使用できなくなり、フィルタ濾過面積が減ることにより、圧損の大幅な増加を引き起こす懸念があることが分かった。
As a result of studies by the present inventors, the technology disclosed in Patent Document 3 has a problem in that since electricity is passed through the honeycomb structure, if condensed water is generated in the exhaust pipe in the exhaust gas, an electrical short circuit will occur. It turns out that there is. It has also been found that there is a problem of electrical short circuits due to the accumulation of carbon particles.
Furthermore, if the technology disclosed in Patent Document 4 is applied to a honeycomb structured filter, some cells will become unusable as gas flow paths, reducing the filter filtration area, which may cause a significant increase in pressure loss. I understand.

本発明は上記問題を勘案してされたものであり、電気加熱によるカーボン微粒子などの燃焼除去が可能であるとともに、凝縮水が発生する位置でも使用可能であり、凝縮水やカーボン堆積による短絡の問題がなく、圧力損失も低いハニカム構造体及び排気ガス浄化装置を提供することを課題とするものである。また、本発明は、上記ハニカム構造体の製造方法を提供することを課題とするものである。 The present invention was developed in consideration of the above problems, and it is possible to burn and remove carbon particles by electric heating, and it can also be used in locations where condensed water is generated. It is an object of the present invention to provide a honeycomb structure and an exhaust gas purification device that are free from problems and have low pressure loss. Another object of the present invention is to provide a method for manufacturing the above honeycomb structure.

本発明者らは鋭意検討の結果、ハニカム構造体の隔壁の表面の少なくとも一部に、磁性体粒子を含み、かつ、通気性を有する表面層を備えることで、上記課題を解決できることを見出した。すなわち、本発明は以下のように特定される。
(1)流体の流路となり、流体の流入側の端面である流入端面から流体の流出側の端面である流出端面まで延びる複数のセルを区画形成する多孔質の隔壁と、
最外周に位置する外周壁と、
を有する柱状のハニカム構造体であって、
前記隔壁の表面の少なくとも一部に表面層を有し、前記表面層が、磁性体粒子を含み、かつ、通気性を有することを特徴とするハニカム構造体。
(2)流体の流路となり、流体の流入側の端面である流入端面から流体の流出側の端面である流出端面まで延びる複数のセルを区画形成する多孔質の隔壁と、
最外周に位置する外周壁と、
を有する柱状のハニカム構造体であって、
前記隔壁の表面の少なくとも一部に表面層を有し、前記表面層が、針状または鱗片状の磁性体粒子を含むことを特徴とするハニカム構造体。
(3)(1)または(2)に記載のハニカム構造体と、
前記ハニカム構造体の外周を螺旋状に周回するコイル配線と、
前記コイル配線の外側に前記コイル配線を排ガス流路内に固定するための固定部材と、
を有する排気ガス浄化装置。
(4)排気消音マフラーと、前記排気消音マフラー内に設けられた、(3)に記載の排気ガス浄化装置と、前記排気消音マフラー内に設けられた消音器とを備えた排気システム。
(5)流体の流路となり、流体の流入側の端面である流入端面から流体の流出側の端面である流出端面まで延びる複数のセルを区画形成する多孔質の隔壁と、
最外周に位置する外周壁と、
を有する柱状のハニカム構造体の製造方法であって、
前記隔壁の表面の少なくとも一部について、磁性体粒子を含み、かつ、通気性を有する表面層を形成する工程を含むことを特徴とするハニカム構造体の製造方法。
As a result of extensive studies, the present inventors have found that the above problem can be solved by providing a surface layer containing magnetic particles and having air permeability on at least a portion of the surface of the partition walls of a honeycomb structure. . That is, the present invention is specified as follows.
(1) A porous partition wall that serves as a fluid flow path and defines a plurality of cells that extend from an inflow end face that is an end face on the fluid inflow side to an outflow end face that is the end face on the fluid outflow side;
an outer peripheral wall located at the outermost periphery;
A columnar honeycomb structure having
A honeycomb structure having a surface layer on at least a part of the surface of the partition wall, the surface layer containing magnetic particles and having air permeability.
(2) a porous partition wall that serves as a fluid flow path and defines a plurality of cells extending from an inflow end face that is an end face on the fluid inflow side to an outflow end face that is the end face on the fluid outflow side;
an outer peripheral wall located at the outermost periphery;
A columnar honeycomb structure having
A honeycomb structure having a surface layer on at least a portion of the surface of the partition wall, the surface layer containing needle-like or scale-like magnetic particles.
(3) The honeycomb structure according to (1) or (2);
a coil wiring spirally surrounding the outer periphery of the honeycomb structure;
a fixing member for fixing the coil wiring in the exhaust gas flow path on the outside of the coil wiring;
An exhaust gas purification device with
(4) An exhaust system including an exhaust silencing muffler, the exhaust gas purification device according to (3) provided in the exhaust silencing muffler, and a muffler provided in the exhaust silencing muffler.
(5) a porous partition that serves as a fluid flow path and defines a plurality of cells that extend from an inflow end face that is an end face on the fluid inflow side to an outflow end face that is the end face on the fluid outflow side;
an outer peripheral wall located at the outermost periphery;
A method for manufacturing a columnar honeycomb structure, comprising:
A method for manufacturing a honeycomb structure, comprising the step of forming a surface layer containing magnetic particles and having air permeability on at least a portion of the surface of the partition wall.

本発明によれば、電気加熱によるカーボン微粒子などの燃焼除去が可能であるとともに、凝縮水が発生する位置でも使用可能であり、凝縮水やカーボン堆積による短絡の問題がなく、圧力損失も低いハニカム構造体及び排気ガス浄化装置を提供することができる。また、本発明によれば、上記ハニカム構造体の製造方法を提供することができる。 According to the present invention, it is possible to burn and remove carbon particles by electrical heating, and the honeycomb can be used even in locations where condensed water is generated, there is no problem of short circuits due to condensed water or carbon deposits, and the pressure loss is low. A structure and an exhaust gas purification device can be provided. Further, according to the present invention, a method for manufacturing the honeycomb structure described above can be provided.

本発明の一実施形態のハニカム構造体を模式的に示す斜視図である。FIG. 1 is a perspective view schematically showing a honeycomb structure according to an embodiment of the present invention. 本発明の一実施形態に係るハニカム構造体が組み込まれた排気ガス浄化装置の排気ガス流路の概略図である。1 is a schematic diagram of an exhaust gas flow path of an exhaust gas purification device incorporating a honeycomb structure according to an embodiment of the present invention. ハニカム構造体の隔壁の表面に表面層が形成された状態を示す模式図である。It is a schematic diagram which shows the state in which the surface layer was formed on the surface of the partition of a honeycomb structure. 実施例7の加熱試験における各誘導加熱周波数30kHz、85kHz、350kHzにおける時間(秒)-温度(℃)の関係を表したグラフである。3 is a graph showing the relationship between time (seconds) and temperature (° C.) at each induction heating frequency of 30 kHz, 85 kHz, and 350 kHz in the heating test of Example 7. 実施例7及び実施例12の加熱試験における時間(秒)-温度(℃)の関係を表したグラフである。2 is a graph showing the relationship between time (seconds) and temperature (° C.) in the heating tests of Examples 7 and 12. 排気消音マフラー内に本発明の一実施形態のハニカム構造体が設けられた排気システムの模式図である。1 is a schematic diagram of an exhaust system in which a honeycomb structure according to an embodiment of the present invention is provided in an exhaust muffler. 排気消音マフラー内に設けられた本発明の一実施形態の排気ガス浄化装置の模式図である。FIG. 1 is a schematic diagram of an exhaust gas purification device according to an embodiment of the present invention provided in an exhaust muffler.

以下、図面を参照して、本発明のハニカム構造体の実施形態について説明するが、本発明は、これに限定されて解釈されるものではなく、本発明の範囲を逸脱しない限りにおいて、当業者の知識に基づいて、種々の変更、修正、改良を加え得るものである。 Hereinafter, embodiments of the honeycomb structure of the present invention will be described with reference to the drawings, but the present invention is not to be construed as being limited thereto. Various changes, modifications, and improvements may be made based on the knowledge of

(1.ハニカム構造体)
図1には、本発明の一実施形態のハニカム構造体を模式的に示す斜視図が記載されている。図示のハニカム構造体1は、最外周に位置する外周壁102と、外周壁102の内側に配設され、第一端面104(流体の流入側の端面である流入端面)から第二端面106(流体の流出側の端面である流出端面)の間に平行に延びる複数のセル(図示では第一端面104が開口して第二端面106に突出する目封止部を有する複数の第1セル108及び第一端面104に突出する目封止部を有し、第二端面106が開口する複数の第2セル110)とを備える。当該複数のセルが、それぞれハニカム構造体1における流体の流路を構成している。また、図示のハニカム構造体1においては、第1セル108及び第2セル110を区画形成する多孔質の隔壁112を備えており、第1セル108及び第2セル110が隔壁112を挟んで交互に隣接配置されており、両端面は市松模様を形成する。図示の実施形態に係るハニカム構造体においては、すべての第1セル108が第2セル110に隣接しており、すべての第2セル110が第1セル108に隣接している。しかしながら、複数のセルは、必ずしも目封止部を有する必要はない。さらに、必ずしもすべての第1セル108が第2セル110に隣接していなくてもよく、必ずしもすべての第2セル110が第1セル108に隣接していなくてもよい。セル108、110の数、配置、形状等及び隔壁112の厚み等は制限されず、必要に応じて適宜設計することができる。
(1. Honeycomb structure)
FIG. 1 is a perspective view schematically showing a honeycomb structure according to an embodiment of the present invention. The illustrated honeycomb structure 1 has an outer peripheral wall 102 located at the outermost periphery, and is disposed inside the outer peripheral wall 102, from a first end face 104 (an inflow end face that is an end face on the fluid inflow side) to a second end face 106 ( A plurality of cells (in the figure, a plurality of first cells 108 having plugging portions in which the first end surface 104 is open and protrudes to the second end surface 106) extend in parallel between the outflow end surface that is the end surface on the fluid outflow side. and a plurality of second cells 110) having plugging portions protruding from the first end surface 104 and having the second end surface 106 open. The plurality of cells each constitute a fluid flow path in the honeycomb structure 1. Further, the illustrated honeycomb structure 1 includes porous partition walls 112 that partition the first cells 108 and the second cells 110, and the first cells 108 and the second cells 110 alternate with each other with the partition walls 112 in between. are arranged adjacent to each other, and both end faces form a checkered pattern. In the honeycomb structure according to the illustrated embodiment, all first cells 108 are adjacent to second cells 110, and all second cells 110 are adjacent to first cells 108. However, the plurality of cells do not necessarily need to have plugging portions. Furthermore, not all first cells 108 need be adjacent to second cells 110, and not all second cells 110 need be adjacent to first cells 108. The number, arrangement, shape, etc. of the cells 108, 110, and the thickness of the partition wall 112, etc. are not limited and can be designed as appropriate.

ハニカム構造体の材質については特に制限はないが、多数の細孔を有する多孔質体であることが必要であるため、通常は、セラミックス材料で形成され、例えば、コージェライト、炭化珪素、チタン酸アルミニウム、窒化珪素、ムライト、アルミナ、珪素-炭化珪素系複合材料、炭化珪素-コージェライト系複合材料の、特に珪素-炭化珪素複合材又は炭化珪素を主成分とする焼結体が挙げられる。本明細書において「炭化珪素系」とは、ハニカム構造体が炭化珪素を、ハニカム構造体全体の50質量%以上含有していることを意味する。ハニカム構造体が珪素-炭化珪素複合材を主成分とするというのは、ハニカム構造体が珪素-炭化珪素複合材(合計質量)を、ハニカム構造体全体の90質量%以上含有していることを意味する。ここで、珪素-炭化珪素複合材は、骨材としての炭化珪素粒子、及び炭化珪素粒子を結合させる結合材としての珪素を含有するものであり、複数の炭化珪素粒子が、炭化珪素粒子間に細孔を形成するようにして、珪素によって結合されていることが好ましい。また、ハニカム構造体が炭化珪素を主成分とするというのは、ハニカム構造体1が炭化珪素(合計質量)を、ハニカム構造体全体の90質量%以上含有していることを意味する。 There are no particular restrictions on the material of the honeycomb structure, but since it needs to be a porous body with a large number of pores, it is usually formed of a ceramic material, such as cordierite, silicon carbide, titanate, etc. Examples include aluminum, silicon nitride, mullite, alumina, silicon-silicon carbide composite materials, silicon carbide-cordierite composite materials, and particularly silicon-silicon carbide composites or sintered bodies containing silicon carbide as a main component. In this specification, "silicon carbide-based" means that the honeycomb structure contains silicon carbide in an amount of 50% or more by mass of the entire honeycomb structure. The honeycomb structure is mainly composed of silicon-silicon carbide composite material, which means that the honeycomb structure contains silicon-silicon carbide composite material (total mass) in an amount of 90% or more by mass of the entire honeycomb structure. means. Here, the silicon-silicon carbide composite material contains silicon carbide particles as an aggregate and silicon as a binder that binds the silicon carbide particles, and a plurality of silicon carbide particles are arranged between the silicon carbide particles. Preferably, they are bonded by silicon in such a way as to form pores. Moreover, the honeycomb structure containing silicon carbide as a main component means that the honeycomb structure 1 contains silicon carbide (total mass) in an amount of 90% or more by mass of the entire honeycomb structure.

好ましくは、ハニカム構造体は、コージェライト、炭化珪素、チタン酸アルミニウム、窒化珪素、ムライト、アルミナからなる群から選択される少なくとも1つのセラミックス材料で形成される。 Preferably, the honeycomb structure is formed of at least one ceramic material selected from the group consisting of cordierite, silicon carbide, aluminum titanate, silicon nitride, mullite, and alumina.

ハニカム構造体のセル形状は特に限定されないが、中心軸に直交する断面において、三角形、四角形、五角形、六角形、八角形等の多角形、円形、又は楕円形であることが好ましく、その他不定形であってもよい。 The cell shape of the honeycomb structure is not particularly limited, but it is preferably a polygon such as a triangle, quadrangle, pentagon, hexagon, or octagon, a circle, or an ellipse in a cross section perpendicular to the central axis, and other irregular shapes. It may be.

また、ハニカム構造体の外形としては、特に限定されないが、端面が円形の柱状(円柱形状)、端面がオーバル形状の柱状、端面が多角形(四角形、五角形、六角形、七角形、八角形等)の柱状等の形状とすることができる。また、ハニカム構造体の大きさは、特に限定されないが、中心軸方向長さが40~500mmが好ましい。また、例えば、ハニカム構造体の外形が円筒状の場合、その端面の半径が50~500mmであることが好ましい。 In addition, the outer shape of the honeycomb structure is not particularly limited, but may be columnar with circular end faces (cylindrical shape), columnar shape with oval end faces, polygonal end faces (square, pentagon, hexagon, heptagon, octagon, etc.). ) can be shaped like a column. Further, the size of the honeycomb structure is not particularly limited, but the length in the central axis direction is preferably 40 to 500 mm. Further, for example, when the outer shape of the honeycomb structure is cylindrical, it is preferable that the radius of the end face is 50 to 500 mm.

ハニカム構造体の隔壁の厚さは、0.20~0.50mmであることが好ましく、製造の容易さの点で、0.25~0.45mmであることが更に好ましい。例えば、0.20mm以上であると、ハニカム構造体の強度がより向上し、0.50mm以下であると、ハニカム構造体をフィルタとして用いた場合に、圧力損失をより小さくすることができる。なお、この隔壁の厚さは、中心軸方向断面を顕微鏡観察する方法で測定した平均値である。 The thickness of the partition walls of the honeycomb structure is preferably 0.20 to 0.50 mm, and more preferably 0.25 to 0.45 mm in terms of ease of manufacture. For example, if it is 0.20 mm or more, the strength of the honeycomb structure is further improved, and if it is 0.50 mm or less, pressure loss can be further reduced when the honeycomb structure is used as a filter. Note that the thickness of the partition wall is an average value measured by observing a cross section in the central axis direction using a microscope.

また、ハニカム構造体を構成する隔壁の気孔率は、30~70%であることが好ましく、製造の容易さの点で40~65%であることが更に好ましい。30%以上であると、圧力損失が減少しやすく、70%以下であると、ハニカム構造体の強度を維持できる。 Further, the porosity of the partition walls constituting the honeycomb structure is preferably 30 to 70%, and more preferably 40 to 65% from the viewpoint of ease of manufacture. When it is 30% or more, pressure loss tends to decrease, and when it is 70% or less, the strength of the honeycomb structure can be maintained.

また、多孔質の隔壁の平均細孔径は、5~30μmであることが好ましく、10~25μmであることが更に好ましい。5μm以上であると、フィルタとして用いた場合に、圧力損失を小さくすることができ、30μm以下であると、ハニカム構造体の強度を維持できる。なお、本明細書において、「平均細孔径」、「気孔率」というときには、水銀圧入法により測定した平均細孔径、気孔率を意味するものとする。 Further, the average pore diameter of the porous partition walls is preferably 5 to 30 μm, more preferably 10 to 25 μm. If it is 5 μm or more, pressure loss can be reduced when used as a filter, and if it is 30 μm or less, the strength of the honeycomb structure can be maintained. In this specification, the terms "average pore diameter" and "porosity" refer to the average pore diameter and porosity measured by mercury porosimetry.

ハニカム構造体のセル密度も特に制限はないが、5~63セル/cm2の範囲であることが好ましく、31~54セル/cm2の範囲であることが更に好ましい。 The cell density of the honeycomb structure is also not particularly limited, but it is preferably in the range of 5 to 63 cells/cm 2 , more preferably in the range of 31 to 54 cells/cm 2 .

このようなハニカム構造体は、セラミックス原料を含有する坏土を、一方の端面から他方の端面まで貫通し流体の流路となる複数のセルを区画形成する隔壁を有するハニカム状に成形して、ハニカム成形体を形成し、このハニカム成形体を、乾燥した後に焼成することによって作製される。そして、このようなハニカム構造体を、本実施形態のハニカム構造体として用いる場合には、外周壁をハニカム構造部と一体的に押し出してそのまま外周壁として使用してもよいし、成形又は焼成後に、ハニカム成形体(ハニカム構造体)の外周を研削して所定形状とし、この外周を研削したハニカム構造体に、コーティング材を塗布して外周コーティングを形成してもよい。なお、本実施形態のハニカム構造体においては、例えば、ハニカム構造体の最外周を研削せずに、外周を有したハニカム構造体を用い、この外周を有するハニカム構造体の外周面(即ち、ハニカム構造体の外周の更に外側)に、更に、上記コーティング材を塗布して、外周コーティングを形成してもよい。即ち、前者の場合には、ハニカム構造体の外周面には、コーティング材からなる外周コーティングのみが最外周に位置する外周壁となり、一方、後者の場合には、ハニカム構造体の外周面に、更にコーティング材からなる外周コーティングが積層された、最外周に位置する、二層構造の外周壁が形成される。外周壁をハニカム構造部と一体的に押し出してそのまま焼成し、外周の加工無しに、外周壁として使用してもよい。 Such a honeycomb structure is produced by forming clay containing a ceramic raw material into a honeycomb shape having partition walls that penetrate from one end face to the other end face and define a plurality of cells that serve as fluid flow paths. It is produced by forming a honeycomb molded body, drying the honeycomb molded body, and then firing the honeycomb molded body. When such a honeycomb structure is used as the honeycomb structure of this embodiment, the outer circumferential wall may be extruded integrally with the honeycomb structure and used as the outer circumferential wall as it is, or it may be extruded after molding or firing. Alternatively, the outer periphery of a honeycomb formed body (honeycomb structure) may be ground into a predetermined shape, and a coating material may be applied to the honeycomb structure whose outer periphery has been ground to form an outer periphery coating. In addition, in the honeycomb structure of this embodiment, for example, the outermost periphery of the honeycomb structure is not ground and a honeycomb structure having an outer periphery is used, and the outer peripheral surface of the honeycomb structure having this outer periphery (i.e., the honeycomb The above-mentioned coating material may be further applied to the outside of the outer periphery of the structure to form an outer periphery coating. That is, in the former case, only the outer peripheral coating made of the coating material becomes the outermost peripheral wall on the outer peripheral surface of the honeycomb structure, while in the latter case, on the outer peripheral surface of the honeycomb structure, Furthermore, a two-layered outer peripheral wall located at the outermost periphery is formed, on which an outer peripheral coating made of a coating material is laminated. The outer peripheral wall may be extruded integrally with the honeycomb structure, fired as it is, and used as the outer peripheral wall without processing the outer periphery.

コーティング材の組成は特に限定されるものではなく、種々の公知のコーティング材を適宜使用することができる。コーティング材は、コロイダルシリカ、有機バインダ、粘土等を更に含有させてもよい。なお、有機バインダは、0.05~0.5質量%用いることが好ましく、0.1~0.2質量%用いることが更に好ましい。また、粘土は、0.2~2.0質量%用いることが好ましく、0.4~0.8質量%用いることが更に好ましい。 The composition of the coating material is not particularly limited, and various known coating materials can be used as appropriate. The coating material may further contain colloidal silica, organic binder, clay, etc. The organic binder is preferably used in an amount of 0.05 to 0.5% by mass, more preferably 0.1 to 0.2% by mass. Further, the clay is preferably used in an amount of 0.2 to 2.0% by mass, more preferably 0.4 to 0.8% by mass.

なお、ハニカム構造体は、隔壁が一体的に形成された一体型のハニカム構造体に限定されることはなく、例えば、図示は省略するが、多孔質の隔壁を有し、隔壁によって流体の流路となる複数のセルが区画形成された柱状のハニカムセグメントが、接合材層を介して複数個組み合わされた構造を有するハニカム構造体(以下、「接合型ハニカム構造体」ということがある)であってもよい。 Note that the honeycomb structure is not limited to an integral honeycomb structure in which partition walls are integrally formed; for example, although not shown, the honeycomb structure may have porous partition walls, and the partition walls may prevent fluid flow A honeycomb structure (hereinafter sometimes referred to as a "bonded honeycomb structure") having a structure in which a plurality of columnar honeycomb segments each having a plurality of cells forming channels are combined via a bonding material layer. There may be.

また、ハニカム構造体は、複数のセルのうちの所定のセルの一方の開口端部と、残余のセルの他方の開口端部とが、目封止部によって目封止されたものであってもよい。このようなハニカム構造体は、排ガスを浄化するフィルタ(ハニカムフィルタ)として用いることができる。なお、このような目封止部は、外周コーティングが形成された後に配設されたものであってもよいし、外周コーティングが形成される前の状態、即ち、ハニカム構造体を作製する段階で配設されたものであってもよい。 Further, in the honeycomb structure, one open end of a predetermined cell among the plurality of cells and the other open end of the remaining cells are plugged with a plugging part. Good too. Such a honeycomb structure can be used as a filter (honeycomb filter) for purifying exhaust gas. Note that such plugging portions may be provided after the outer peripheral coating is formed, or may be provided before the outer peripheral coating is formed, that is, at the stage of manufacturing the honeycomb structure. It may be arranged.

このような目封止部は、従来公知のハニカム構造体の目封止部として用いられるものと同様に構成されたものを用いることができる。 As such a plugging part, a plugging part configured similarly to that used as a plugging part of a conventionally known honeycomb structure can be used.

また、本実施形態のハニカム構造体は、隔壁の表面及び隔壁の細孔の内部の少なくとも一方に、触媒が担持されたものであってもよい。このように、本実施形態のハニカム構造体は、触媒を担持した触媒担体や、排ガス中の粒状物質(カーボン微粒子)を浄化するために目封止部を設けたフィルタ(例えば、ディーゼルパティキュレートフィルタ(以下、「DPF」ともいう))として構成されたものであってもよい。 Further, in the honeycomb structure of the present embodiment, a catalyst may be supported on at least one of the surfaces of the partition walls and the insides of the pores of the partition walls. In this way, the honeycomb structure of the present embodiment can be used as a catalyst carrier supporting a catalyst, or as a filter (for example, a diesel particulate filter) provided with plugging portions to purify particulate matter (carbon particles) in exhaust gas. (hereinafter also referred to as "DPF")).

触媒の種類については特に制限なく、ハニカム構造体の使用目的や用途に応じて適宜選択することができる。例えば、貴金属系触媒又はこれら以外の触媒が挙げられる。貴金属系触媒としては、白金(Pt)、パラジウム(Pd)、ロジウム(Rh)といった貴金属をアルミナ細孔表面に担持し、セリア、ジルコニア等の助触媒を含む三元触媒や酸化触媒、又は、アルカリ土類金属と白金を窒素酸化物(NOx)の吸蔵成分として含むNOx吸蔵還元触媒が例示される。貴金属を用いない触媒として、銅置換又は鉄置換ゼオライトを含むNOx選択還元触媒等が例示される。なお、触媒の担持方法についても特に制限はなく、従来、ハニカム構造体に触媒を担持する担持方法に準じて行うことができる。 The type of catalyst is not particularly limited, and can be appropriately selected depending on the purpose and use of the honeycomb structure. Examples include noble metal catalysts and catalysts other than these. Examples of noble metal catalysts include three-way catalysts, oxidation catalysts, and alkali catalysts that support noble metals such as platinum (Pt), palladium (Pd), and rhodium (Rh) on the surface of alumina pores, and include promoters such as ceria and zirconia. An NO x storage reduction catalyst containing an earth metal and platinum as nitrogen oxide (NO x ) storage components is exemplified. Examples of catalysts that do not use noble metals include NO x selective reduction catalysts containing copper-substituted or iron-substituted zeolites. Note that there is no particular restriction on the method of supporting the catalyst, and it can be carried out in accordance with the conventional method of supporting the catalyst on a honeycomb structure.

焼成ハニカム構造体のそれぞれをハニカムセグメントとして利用し、複数のハニカムセグメントの側面同士を接合材で接合して一体化し、ハニカムセグメントが接合された状態のハニカム構造体とすることができる。ハニカムセグメントが接合された状態のハニカム構造体は例えば以下のように製造することができる。各ハニカムセグメントの両端面に接合材付着防止用マスクを貼り付けた状態で、接合面(側面)に接合材を塗工する。 Each of the fired honeycomb structures can be used as a honeycomb segment, and the side surfaces of a plurality of honeycomb segments can be joined and integrated with a bonding material to form a honeycomb structure in which the honeycomb segments are joined. A honeycomb structure in which honeycomb segments are joined can be manufactured, for example, as follows. A bonding material is applied to the bonding surface (side surface) with a bonding material adhesion prevention mask attached to both end faces of each honeycomb segment.

次に、これらのハニカムセグメントを、ハニカムセグメントの互いの側面同士が対向するように隣接して配置し、隣接するハニカムセグメント同士を圧着した後、加熱乾燥する。このようにして、隣接するハニカムセグメントの側面同士が接合材によって接合されたハニカム構造体を作製する。ハニカム構造体に対しては、外周部を研削加工して所望の形状(例えば円柱状)とし、外周面にコーティング材を塗工した後、加熱乾燥させて外周壁を形成してもよい。 Next, these honeycomb segments are arranged adjacently so that the side surfaces of the honeycomb segments face each other, and after the adjacent honeycomb segments are pressed together, they are heated and dried. In this way, a honeycomb structure is produced in which the side surfaces of adjacent honeycomb segments are joined by the joining material. For the honeycomb structure, the outer circumferential portion may be ground to a desired shape (for example, cylindrical), a coating material may be applied to the outer circumferential surface, and then the outer circumferential wall may be formed by heating and drying.

接合材付着防止用マスクの材料は、特に制限はないが、例えばポリプロピレン(PP)、ポリエチレンテレフタレート(PET)、ポリイミド、又はテフロン(登録商標)等の合成樹脂を好適に使用可能である。また、マスクは粘着層を備えていることが好ましく、粘着層の材料は、アクリル系樹脂、ゴム系(例えば、天然ゴム又は合成ゴムを主成分とするゴム)、又はシリコン系樹脂であることが好ましい。 The material of the bonding material adhesion prevention mask is not particularly limited, but for example, synthetic resins such as polypropylene (PP), polyethylene terephthalate (PET), polyimide, or Teflon (registered trademark) can be suitably used. Further, the mask preferably includes an adhesive layer, and the material of the adhesive layer may be acrylic resin, rubber-based (for example, rubber whose main component is natural rubber or synthetic rubber), or silicone-based resin. preferable.

接合材付着防止用マスクとしては、例えば厚みが20~50μmの粘着フィルムを好適に使用することができる。 As the mask for preventing adhesion of bonding material, for example, an adhesive film having a thickness of 20 to 50 μm can be suitably used.

接合材としては、例えば、セラミックス粉末、分散媒(例えば、水等)、及び必要に応じて、バインダ、解膠剤、発泡樹脂等の添加剤を混合することによって調製したものを用いることができる。セラミックスとしては、コージェライト、ムライト、ジルコン、チタン酸アルミニウム、炭化珪素、窒化珪素、ジルコニア、スピネル、インディアライト、サフィリン、コランダム、及びチタニアからなる群から選ばれる少なくとも1種を含有するセラミックスであることが好ましく、ハニカム構造体と同材質であることがより好ましい。バインダとしては、ポリビニルアルコールやメチルセルロース、CMC(カルボキシメチルセルロース)などを挙げることができる。 As the bonding material, for example, a material prepared by mixing ceramic powder, a dispersion medium (e.g., water, etc.), and, if necessary, additives such as a binder, a deflocculant, and a foamed resin, can be used. . The ceramic must contain at least one member selected from the group consisting of cordierite, mullite, zircon, aluminum titanate, silicon carbide, silicon nitride, zirconia, spinel, indialite, sapphirine, corundum, and titania. is preferable, and it is more preferable that the material is the same as that of the honeycomb structure. Examples of the binder include polyvinyl alcohol, methylcellulose, and CMC (carboxymethylcellulose).

図2は、ハニカム構造体が組み込まれた排気ガス浄化装置の排気ガス流路の概略図である。排気ガスの流路は、金属管2により定められる。金属管2の拡径部2aに排気ガス浄化装置6が配置される。排気ガス浄化装置6は、ハニカム構造体1、ハニカム構造体1の外周を螺旋状に周回するコイル配線4、コイル配線4を金属管2内に固定するための固定部材5を有する。ハニカム構造体1は触媒を担持してもよい。 FIG. 2 is a schematic diagram of an exhaust gas flow path of an exhaust gas purification device incorporating a honeycomb structure. The exhaust gas flow path is defined by the metal tube 2. An exhaust gas purification device 6 is arranged in the enlarged diameter portion 2 a of the metal tube 2 . The exhaust gas purification device 6 includes a honeycomb structure 1 , a coil wiring 4 spirally surrounding the outer periphery of the honeycomb structure 1 , and a fixing member 5 for fixing the coil wiring 4 inside the metal tube 2 . The honeycomb structure 1 may support a catalyst.

コイル配線4は、ハニカム構造体1の外周に螺旋状に巻かれる。2以上のコイル配線4が用いられる形態も想定される。スイッチSWのオン(ON)に応じて交流電源CSから供給される交流電流がコイル配線4に流れ、この結果として、コイル配線4の周囲には周期的に変化する磁界が生じる。なお、スイッチSWのオン・オフが制御部3により制御される。制御部3は、エンジンの始動に同期してスイッチSWをオンさせ、コイル配線4に交流電流を流すことができる。なお、エンジンの始動とは無関係に(例えば、運転手により押される加熱スイッチの作動に応じて)制御部3がスイッチSWをオンする形態も想定される。固定部材5は、耐熱性部材であり、触媒を担持したハニカム構造体1及びコイル配線4を金属管2内に固定するために設けられる。
排気ガス浄化装置が印加する投入電力としては、加熱性能の観点から、1kW~10kWの範囲であることが好ましい。また、加熱周波数としては、10~500kHzの範囲であることが好ましい。
The coil wiring 4 is spirally wound around the outer periphery of the honeycomb structure 1. A configuration in which two or more coil wirings 4 are used is also envisioned. When the switch SW is turned ON, an alternating current supplied from the alternating current power source CS flows through the coil wiring 4, and as a result, a periodically changing magnetic field is generated around the coil wiring 4. Note that the on/off of the switch SW is controlled by the control section 3. The control unit 3 can turn on the switch SW in synchronization with the start of the engine and cause an alternating current to flow through the coil wiring 4. Note that a configuration in which the control unit 3 turns on the switch SW regardless of engine starting (for example, in response to activation of a heating switch pressed by the driver) is also envisioned. The fixing member 5 is a heat-resistant member and is provided to fix the honeycomb structure 1 supporting the catalyst and the coil wiring 4 inside the metal tube 2 .
The input power applied by the exhaust gas purification device is preferably in the range of 1 kW to 10 kW from the viewpoint of heating performance. Further, the heating frequency is preferably in the range of 10 to 500 kHz.

本開示においては、コイル配線4に流れる交流電流に応じた磁界の変化に応じてハニカム構造体1が昇温する。これによりハニカム構造体1により捕集されるカーボン微粒子などが燃焼する。また、ハニカム構造体1が触媒を担持する場合、ハニカム構造体1の昇温は、ハニカム構造体1に含まれる触媒担体より担持された触媒の温度を高め、触媒反応が促進される。端的には、一酸化炭素(CO)、窒化酸化物(NOx)、炭化水素(CH)が、二酸化炭素(CO2)、窒素(N2)、水(H2O)に酸化又は還元される。 In the present disclosure, the temperature of the honeycomb structure 1 increases according to changes in the magnetic field according to the alternating current flowing through the coil wiring 4. As a result, carbon particles and the like collected by the honeycomb structure 1 are burned. Further, when the honeycomb structure 1 supports a catalyst, increasing the temperature of the honeycomb structure 1 increases the temperature of the supported catalyst more than the catalyst carrier included in the honeycomb structure 1, and the catalytic reaction is promoted. In short, carbon monoxide (CO), nitride oxides (NO x ), and hydrocarbons (CH) are oxidized or reduced to carbon dioxide (CO 2 ), nitrogen (N 2 ), and water (H 2 O). Ru.

図6は、排気消音マフラー22と、排気消音マフラー22内に設けられた、排気ガス浄化装置26とを備えた排気システム20の模式図である。排気消音マフラー22には消音器が設けられている。消音器は、メイン消音器及びサブ消音器などの複数の消音器で構成されていてもよい。排気ガス浄化装置26は、ハニカム構造体1が組み込まれており、ハニカム構造体1の外周を螺旋状に周回するコイル配線、コイル配線を排ガス流路内に固定するための固定部材を有する。排気システム20は、排気消音マフラー22へ供給される排ガスの流路、または、排気消音マフラー22から排出される排ガスの流路となる排気管21を備えている。 FIG. 6 is a schematic diagram of an exhaust system 20 including an exhaust silencing muffler 22 and an exhaust gas purification device 26 provided within the exhaust silencing muffler 22. The exhaust muffler 22 is provided with a muffler. The muffler may include a plurality of mufflers such as a main muffler and a sub muffler. The exhaust gas purification device 26 has the honeycomb structure 1 incorporated therein, and has a coil wiring that spirals around the outer periphery of the honeycomb structure 1 and a fixing member for fixing the coil wiring in the exhaust gas flow path. The exhaust system 20 includes an exhaust pipe 21 that serves as a flow path for exhaust gas supplied to the exhaust silencing muffler 22 or a flow path for exhaust gas discharged from the exhaust silencing muffler 22.

図7に、排気システム20の排気消音マフラー22内に設けられた排気ガス浄化装置26の模式図を示す。また、図7には、消音機能を説明するための、排気ガス浄化装置26の保持マット25に埋め込まれたコイル配線24近傍の一部の拡大図が記載されている。排気システム20において、ハニカム構造体1内を通過するガス温度が低いほど、ガスの堆積流量が小さくなり、ハニカム構造体1の隔壁を通過するガス速度を小さくすることができる。このため、排気システム20のできるだけ下流側にハニカム構造体1を配置することがスス捕集効率を確保する観点から好ましい。また、排気システム20の最下流にあるメイン消音器やその前段の補助マフラーの内部にハニカム構造体1を設けることが好ましい。従来のハニカム構造体を排気消音マフラー内に搭載すると、水の凝縮によりハニカム構造体の隔壁の小細孔のみが毛細管現象により液体の水で塞がれる。その結果、大細孔に集中して高速のガスが流れることでスス捕集効率が悪化する問題や、排ガス温度が低すぎてススが再生できない問題などがあった。これに対し、ハニカム構造体1は電磁誘導加熱により水を蒸発除去することができるので、スス捕集効率を高く維持することが可能であるとともに、スス再生時のスス再生に必要な温度まで加熱することができる。このため、ススが再生できない問題が生じにくい。ハニカム構造体1はガスの拡流、縮流、ガスの多孔質体通過、セル流路通過等の圧力損失要因を有し、これらは消音効果を有する。このため、消音器内の消音機能の一部代替が可能である。高周波数音の低減効果を強化するため、図7のように排気消音マフラー22の外周近傍に高周波数音を閉じ込め、その中で減衰させる方法がさらに有効である。図7に示すとおり、ハニカム構造体外周近傍セルは両端が封止された構造となっており、軸方向に音波は漏れにくい。図7の拡大図部分に示すように、排気システム20の排気消音マフラー22内のハニカム構造体1内に伝わる音波は、ハニカム構造体1の隔壁112及び隔壁112間の空隙を伝わり、隔壁によって減衰されながら進行し、保持マット25に接する最外周の隔壁112において跳ね返される。このようにして、音波が外部へ伝播することを抑制している。ハニカム構造体としては、図7に示されているように目封じの無いセルが貫通しているものでも良く、両端を交互に目封止したウォールフロー型フィルタであってもよい。消音効果の観点からは、両端を交互に目封止したウォールフロー型フィルタの方がより好ましい。 FIG. 7 shows a schematic diagram of the exhaust gas purification device 26 provided in the exhaust muffler 22 of the exhaust system 20. Further, FIG. 7 shows an enlarged view of a part of the vicinity of the coil wiring 24 embedded in the holding mat 25 of the exhaust gas purification device 26 for explaining the silencing function. In the exhaust system 20, the lower the temperature of the gas passing through the honeycomb structure 1, the lower the gas deposition flow rate, and the lower the gas velocity passing through the partition walls of the honeycomb structure 1. For this reason, it is preferable to arrange the honeycomb structure 1 as downstream of the exhaust system 20 as possible from the viewpoint of ensuring soot collection efficiency. Further, it is preferable to provide the honeycomb structure 1 inside the main muffler located at the most downstream side of the exhaust system 20 or the auxiliary muffler at the preceding stage thereof. When a conventional honeycomb structure is mounted in an exhaust muffler, only the small pores in the partition walls of the honeycomb structure are filled with liquid water due to capillary action due to water condensation. As a result, there were problems such as the soot collection efficiency being deteriorated due to high-speed gas flowing concentrated in large pores, and the exhaust gas temperature being too low for soot to be regenerated. On the other hand, since the honeycomb structure 1 can evaporate water by electromagnetic induction heating, it is possible to maintain high soot collection efficiency, and it can also be heated to the temperature required for soot regeneration during soot regeneration. can do. Therefore, the problem of not being able to regenerate soot is less likely to occur. The honeycomb structure 1 has pressure loss factors such as gas expansion, gas contraction, gas passage through a porous body, and passage through cell channels, and these have a noise-reducing effect. Therefore, it is possible to partially replace the silencing function in the muffler. In order to enhance the effect of reducing high-frequency sounds, it is more effective to confine high-frequency sounds near the outer periphery of the exhaust muffler 22 and attenuate them therein, as shown in FIG. As shown in FIG. 7, the cells near the outer periphery of the honeycomb structure have a structure in which both ends are sealed, so that sound waves are unlikely to leak in the axial direction. As shown in the enlarged view of FIG. 7, the sound waves transmitted within the honeycomb structure 1 in the exhaust muffler 22 of the exhaust system 20 are transmitted through the partition walls 112 of the honeycomb structure 1 and the gaps between the partition walls 112, and are attenuated by the partition walls. It advances while being held by the holding mat 25, and is bounced off at the outermost partition wall 112 that is in contact with the holding mat 25. In this way, propagation of sound waves to the outside is suppressed. The honeycomb structure may be one in which unplugged cells pass through it as shown in FIG. 7, or it may be a wall flow type filter in which both ends are alternately plugged. From the viewpoint of sound deadening effect, a wall flow type filter in which both ends are alternately plugged is more preferable.

(2.表面層)
図3に示されるように、ハニカム構造体1は、その隔壁112の表面の少なくとも一部において、表面層114を有する。表面層114は、磁性体粒子116を含み、かつ、通気性を有する。
(2. Surface layer)
As shown in FIG. 3, the honeycomb structure 1 has a surface layer 114 on at least a portion of the surface of the partition walls 112. The surface layer 114 includes magnetic particles 116 and has air permeability.

ここで、通気性を有するとは、表面層のパーミアビリティーが、1.0×10-132以上であることをいう。圧力損失をさらに低減する観点から、パーミアビリティーが、1.0×10-122以上であることが好ましい。表面層が通気性を有することで、表面層に起因する圧力損失を抑制することができる。 Here, having air permeability means that the permeability of the surface layer is 1.0×10 −13 m 2 or more. From the viewpoint of further reducing pressure loss, it is preferable that the permeability is 1.0×10 −12 m 2 or more. When the surface layer has air permeability, pressure loss caused by the surface layer can be suppressed.

また、本明細書において「パーミアビリティー」は、下記式(1)により算出される物性値をいい、所定のガスがその物(隔壁)を通過する際の通過抵抗を表す指標となる値である。ここで、下記式(1)中、Cはパーミアビリティー(m2)、Fはガス流量(cm3/s)、Tは試料厚み(cm)、Vはガス粘性(dynes・sec/cm2)、Dは試料直径(cm)、Pはガス圧力(PSI)を示す。なお、下記式(1)中の数値は、13.839(PSI)=1(atm)であり、68947.6(dynes・sec/cm2)=1(PSI)である。 In addition, in this specification, "permeability" refers to a physical property value calculated by the following formula (1), and is a value that is an index representing the passage resistance when a given gas passes through that object (partition wall). . Here, in the following formula (1), C is permeability (m 2 ), F is gas flow rate (cm 3 /s), T is sample thickness (cm), and V is gas viscosity (dynes・sec/cm 2 ). , D is the sample diameter (cm), and P is the gas pressure (PSI). Note that the numerical values in the following formula (1) are 13.839 (PSI) = 1 (atm), and 68947.6 (dynes·sec/cm 2 ) = 1 (PSI).

Figure 0007423532000001
パーミアビリティーを測定する際には、表面層つきの隔壁を切り出し、この表面層つきの状態で、パーミアビリティーを測定した後、表面層を削りとった状態でのパーミアビリティー測定を行い、表面層と隔壁基材の厚さの比率と、これらのパーミアビリティー測定結果から、表面層のパーミアビリティーを算出する。
Figure 0007423532000001
When measuring permeability, cut out the partition wall with the surface layer, measure the permeability with this surface layer attached, and then measure the permeability with the surface layer scraped off. The permeability of the surface layer is calculated from the material thickness ratio and these permeability measurement results.

表面層114が磁性体粒子116を含むことで、ハニカム構造体1は電磁誘導により加熱される。そのため、ハニカム構造体1自体に電気を流す必要がなく、凝縮水が発生する環境でも短絡の発生を抑制することができる。また、カーボン堆積による短絡も抑制できる。この効果を得るには、ハニカム構造体1の隔壁112の表面の少なくとも一部において上記表面層114を設ける必要がある。なお、図3では隔壁112の両面が表面層114に覆われているが、必ずしも両面に形成する必要はなく、例えば第1セル108又は第2セル110を形成する面のみに表面層114を形成してもよい。すなわち、表面層114は、少なくとも隔壁112の片側を覆うことが好ましい。 Since the surface layer 114 includes the magnetic particles 116, the honeycomb structure 1 is heated by electromagnetic induction. Therefore, there is no need to supply electricity to the honeycomb structure 1 itself, and it is possible to suppress the occurrence of short circuits even in an environment where condensed water is generated. Furthermore, short circuits due to carbon deposition can also be suppressed. In order to obtain this effect, it is necessary to provide the surface layer 114 on at least a portion of the surface of the partition walls 112 of the honeycomb structure 1. Note that although both sides of the partition wall 112 are covered with the surface layer 114 in FIG. 3, it is not necessarily necessary to form the surface layer 114 on both sides. You may. That is, it is preferable that the surface layer 114 covers at least one side of the partition wall 112.

磁性体粒子116を含む表面層114は、そのスス再生効果を最も発揮しやすい部位のみに設けてもよい。例えば、通常のガソリンパティキュレータの初期のスス堆積はハニカム構造体1の出口近傍に多めに発生する。このため、ハニカム構造体1の下流側領域のみに表面層114を設けてもよい。このような構成によれば、ススが多く堆積している部位のみを加熱するため、ススの燃焼を効率的に行うことができ、消費電力量を抑えることができる。特に、停車時のようにハニカム構造体1にガスが流れていない状況でススを再生することに適する。また、ハニカム構造体1にガスが流れている状況でも効率良くススの燃焼を行うため、ガスの流れ方向(ハニカム構造体1の軸方向)の中央部のみに表面層114を設けてもよい。ガスの流れ方向の中央部を加熱することにより、ガスによる熱伝達の効果も利用して、ススの堆積量が多いハニカム構造体1の下流領域のススを効果的に燃焼させることができる。 The surface layer 114 containing the magnetic particles 116 may be provided only in a region where its soot regeneration effect is most likely to be exhibited. For example, a large amount of soot builds up in the initial stage of a normal gasoline particulater near the outlet of the honeycomb structure 1. For this reason, the surface layer 114 may be provided only in the downstream region of the honeycomb structure 1. According to such a configuration, since only the portion where a large amount of soot has accumulated is heated, soot can be burned efficiently and power consumption can be suppressed. In particular, it is suitable for regenerating soot in a situation where gas is not flowing through the honeycomb structure 1, such as when the vehicle is stopped. Furthermore, in order to efficiently burn soot even when gas is flowing through the honeycomb structure 1, the surface layer 114 may be provided only in the central portion in the gas flow direction (axial direction of the honeycomb structure 1). By heating the central portion in the flow direction of the gas, the soot in the downstream region of the honeycomb structure 1 where a large amount of soot is deposited can be effectively combusted by also utilizing the effect of heat transfer by the gas.

磁性体粒子116は、好ましくはキュリー温度を有する磁性体で形成されている。磁性体粒子116のキュリー温度は特に限定されないが、好ましくは450℃を超えるものである。より好ましくは、800℃以上である。磁性体粒子116のキュリー温度が450℃を超えれば、触媒活性温度以上に触媒温度を上昇させるのに十分なハニカム温度に達することが可能になる。450℃のキュリー温度を超える磁性体粒子116の組成として、例えばCr18%Fe(Cr18質量%のステンレス)、Fe、Fe-Cr-Al合金、Fe-Cr-Si合金、Fe-Si-Ti合金、Co-Fe合金、Co-Fe-V合金、Co-Ni-Fe合金、Fe-Co-Nb合金、Fe-Co-Cr合金、Fe-Co-Cr-Mo合金、Fe-Co-Cr-Mo-Al合金、FeOFe23、NiOFe23、CuOFe23、MgOFe23、MnBi、Ni、MnSb、MnOFe23、Y3Fe512等がある。キュリー温度が800℃以上の磁性体粒子としては、Co-Fe合金、Co-Fe-V合金、Co-Ni-Fe合金、Fe-Co-Nb合金、Fe-Co-Cr合金、Fe-Co-Cr-Mo合金、Fe-Co-Cr-Mo-Al合金などが挙げられる。具体的な組成としては、残部Co-20質量%Fe、残部Co-25質量%Ni-4質量%Fe、残部Fe-15~35質量%Co、残部Fe-17質量%Co-2質量%Cr-1質量%Mo、残部Fe-49質量%Co-2質量%V、残部Fe-18質量%Co-10質量%Cr-2質量%Mo-1質量%Al、残部Fe-27質量%Co-1質量%Nb、残部Fe-20質量%Co-1質量%Cr-2質量%V、残部Fe-35質量%Co-1質量%Cr、純コバルト、純鉄、電磁軟鉄、残部Fe-0.1~0.5質量%Mn等がある。キュリー温度が高いCoを含む金属を用いることが望ましい。 The magnetic particles 116 are preferably made of a magnetic material having a Curie temperature. The Curie temperature of the magnetic particles 116 is not particularly limited, but preferably exceeds 450°C. More preferably, the temperature is 800°C or higher. If the Curie temperature of the magnetic particles 116 exceeds 450° C., it becomes possible to reach a honeycomb temperature sufficient to raise the catalyst temperature above the catalyst activation temperature. Examples of the composition of the magnetic particles 116 having a Curie temperature of 450° C. include Cr18%Fe (Cr18% by mass stainless steel), Fe, Fe-Cr-Al alloy, Fe-Cr-Si alloy, Fe-Si-Ti alloy, Co-Fe alloy, Co-Fe-V alloy, Co-Ni-Fe alloy, Fe-Co-Nb alloy, Fe-Co-Cr alloy, Fe-Co-Cr-Mo alloy, Fe-Co-Cr-Mo- Examples include Al alloy, FeOFe 2 O 3 , NiOFe 2 O 3 , CuOFe 2 O 3 , MgOFe 2 O 3 , MnBi, Ni, MnSb, MnOFe 2 O 3 , Y 3 Fe 5 O 12 and the like. Examples of magnetic particles having a Curie temperature of 800°C or higher include Co-Fe alloy, Co-Fe-V alloy, Co-Ni-Fe alloy, Fe-Co-Nb alloy, Fe-Co-Cr alloy, and Fe-Co- Examples include Cr-Mo alloy and Fe-Co-Cr-Mo-Al alloy. The specific composition is: balance Co-20 mass% Fe, balance Co-25 mass% Ni-4 mass% Fe, balance Fe-15 to 35 mass% Co, balance Fe-17 mass% Co-2 mass% Cr. -1% by mass Mo, remainder Fe-49% by mass Co-2% by mass V, remainder Fe-18% by mass Co-10% by mass Cr-2% by mass Mo-1% by mass Al, remainder Fe-27% by mass Co- 1 mass% Nb, balance Fe-20 mass% Co-1 mass% Cr-2 mass% V, balance Fe-35 mass% Co-1 mass% Cr, pure cobalt, pure iron, electromagnetic soft iron, balance Fe-0. 1 to 0.5% by mass Mn, etc. It is desirable to use a metal containing Co which has a high Curie temperature.

表面層114の気孔率は、50%以上であることが好ましく、60%以上がより好ましく、70%以上がさらに好ましい。50%以上の気孔率を有することで、圧力損失を抑えることができる。ただし、気孔率が高すぎると表面層が脆くなり、はがれやすくなるので、90%以下とすることが好ましい。
水銀圧入法により表面層114の気孔率を測定する方法として、表面層が形成された基材での水銀ポロシカーブと表面層のみを削って取り除いた基材のみの水銀ポロシカーブとの差を表面層の水銀ポロシカーブとみなし、削りとった質量と水銀ポロシカーブとから表面層の気孔率が算出される。SEM画像撮影を行い、表面層部分の画像解析により、空隙部と個体部の面積比率から表面層の気孔率を算出しても良い。
The porosity of the surface layer 114 is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more. By having a porosity of 50% or more, pressure loss can be suppressed. However, if the porosity is too high, the surface layer becomes brittle and easily peels off, so it is preferably 90% or less.
As a method of measuring the porosity of the surface layer 114 by mercury porosimetry, the difference between the mercury porosicarb of the base material on which the surface layer is formed and the mercury porosicarb of the base material only from which only the surface layer has been removed by scraping is calculated. It is regarded as mercury porosicarb, and the porosity of the surface layer is calculated from the scraped mass and mercury porosicarb. The porosity of the surface layer may be calculated from the area ratio of voids and solid portions by taking a SEM image and analyzing the image of the surface layer portion.

また、表面層114の平均細孔直径は、10μm以下であることが好ましく、5μm以下であることがより好ましく、4μm以下であることがさらに好ましく、3μm以下であることが特に好ましい。平均細孔直径を10μm以下とすることで、高い粒子捕集効率を達成することができる。ただし、表面層114の平均細孔直径が小さすぎると圧力損失が増加してしまうので、0.5μm以上とすることが好ましい。 Further, the average pore diameter of the surface layer 114 is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 4 μm or less, and particularly preferably 3 μm or less. High particle collection efficiency can be achieved by setting the average pore diameter to 10 μm or less. However, if the average pore diameter of the surface layer 114 is too small, pressure loss will increase, so it is preferably 0.5 μm or more.

水銀圧入法により表面層114の平均細孔直径を測定する方法として、水銀ポロシメータでのピーク値という形にして、表面層が形成された基材での水銀ポロシカーブ(細孔容積頻度)と表面層114のみを削って取り除いた基材のみの水銀ポロシカーブとの差を表面層の水銀ポロシカーブとし、そのピークを平均細孔直径とする。また、ハニカム構造体の断面のSEM画像を撮影し表面層部分の画像解析により、空隙部と個体部の2値化を行い、ランダムに20以上の空隙を選択してその内接円の平均を平均細孔直径としても良い。 As a method of measuring the average pore diameter of the surface layer 114 by mercury porosimetry, the peak value in a mercury porosimeter is measured, and the mercury porosicarb (pore volume frequency) of the base material on which the surface layer is formed and the surface layer The difference between the mercury porosicarb of the base material only and the surface layer mercury porosicarb obtained by scraping off only 114 is taken as the mercury porosicarb of the surface layer, and the peak thereof is taken as the average pore diameter. In addition, we took a SEM image of the cross section of the honeycomb structure and analyzed the image of the surface layer to binarize the voids and solid parts, randomly selected 20 or more voids, and calculated the average of their inscribed circles. It may also be the average pore diameter.

表面層114における磁性体粒子116の重量平均粒子径は20μm以下であることが好ましい。重量平均粒子径を20μm以下とすることで、目標とする表面層の平均細孔直径、厚さ、気孔率を全て満足する範囲におさめることが、他のコントロール可能な設計因子との組み合わせで可能となる。なお、磁性体粒子116の重量平均粒子径の下限は特に設けないが、例えば0.5μm以上とすることができる。なお、重量平均粒子径は、レーザー回折式粒度分布測定装置で測定するものとする。 The weight average particle diameter of the magnetic particles 116 in the surface layer 114 is preferably 20 μm or less. By setting the weight average particle diameter to 20 μm or less, it is possible to keep the target average pore diameter, thickness, and porosity of the surface layer within a range that satisfies all of them, in combination with other controllable design factors. becomes. Note that there is no particular lower limit to the weight average particle diameter of the magnetic particles 116, but it can be set to, for example, 0.5 μm or more. In addition, the weight average particle diameter shall be measured with a laser diffraction type particle size distribution analyzer.

また、図3では表面層114と隔壁112の厚みが同程度であるが、表面層114の厚みは特に限定されない。ただし、表面層114の効果をより顕著に得るためには、表面層114の厚みが10μm以上であることが好ましい。一方、圧力損失の増加を回避する観点から、表面層114の厚みが80μm以下であることが好ましい。表面層114の厚みはより好ましくは50μm以下である。表面層の厚みの測定方法として、例えば表面層が形成されたハニカム構造体を、セルが伸びる方向に垂直な方向に切断して、その断面から表面層の厚みを測定し、任意の5点の厚みの測定値の平均を取ることができる。 Moreover, although the thickness of the surface layer 114 and the partition wall 112 are approximately the same in FIG. 3, the thickness of the surface layer 114 is not particularly limited. However, in order to obtain more remarkable effects of the surface layer 114, it is preferable that the thickness of the surface layer 114 is 10 μm or more. On the other hand, from the viewpoint of avoiding an increase in pressure loss, the thickness of the surface layer 114 is preferably 80 μm or less. The thickness of the surface layer 114 is more preferably 50 μm or less. As a method for measuring the thickness of the surface layer, for example, a honeycomb structure with a surface layer formed thereon is cut in a direction perpendicular to the direction in which the cells extend, and the thickness of the surface layer is measured from the cross section. The thickness measurements can be averaged.

また、磁性体粒子は、磁性体粒子116の最短径dが0.1~5μmであり、磁性体粒子116の最長径をLμmとしたとき、L/d≧3であることが好ましい。これにより、電気伝導性を保ちつつ、通気性を十分に確保し、且つ、スス捕集効率の高い表面層の微構造が確保できる。最短径dとは、SEM撮影画像からの画像解析により50粒子について粒子の最長径に直交する線分のうち最大となる線分をその粒子における最短径とし、これを粒子の数で平均することで、最短径dを求められるものである。長さとは、SEM画像において50以上の粒子の最長径を粒子の数で平均することで、最長径Lを求められる。好ましくは、磁性体粒子116が針状または鱗片状である。針状とは、L/d≧5をいう。鱗片状とは、磁性体粒子116の厚さtと最長径Lとの比L/t>5をいう。磁性体粒子116の厚さtは、SEM撮影画像からの画像解析により50粒子について粒子の最も厚さが大きい部位の当該厚さを測定し、これを粒子の数で平均することで求められる。 Further, it is preferable that the shortest diameter d of the magnetic particles 116 is 0.1 to 5 μm, and L/d≧3, where the longest diameter of the magnetic particles 116 is L μm. Thereby, it is possible to ensure sufficient air permeability while maintaining electrical conductivity, and a microstructure of the surface layer with high soot trapping efficiency. The shortest diameter d is defined as the shortest diameter of the particle, which is the largest line segment perpendicular to the longest diameter of 50 particles based on image analysis from SEM images, and is averaged by the number of particles. Then, the shortest diameter d can be found. As for length, the longest diameter L can be obtained by averaging the longest diameters of 50 or more particles in the SEM image by the number of particles. Preferably, the magnetic particles 116 are needle-shaped or scale-shaped. Acicular shape means L/d≧5. The term "scaly" refers to a ratio L/t>5 between the thickness t and the longest diameter L of the magnetic particles 116. The thickness t of the magnetic particles 116 is determined by measuring the thickness of the thickest portion of 50 particles by image analysis from the SEM photographed image, and averaging the thickness by the number of particles.

表面層114と、隔壁112の間には、表面層114の熱膨張係数及び隔壁112の熱膨張係数の間にある熱膨張係数を有する応力緩和層を設けることが好ましい。これにより、表面層114と隔壁112の熱膨張係数の差によるクラックなどの発生を防止することができ、耐熱衝撃性が向上する。応力緩和層の組成は特に限定されないが、例えば低膨張ガラス層、アルミナ層、シリカ層、セリア層を好適に用いることができる。 A stress relaxation layer having a thermal expansion coefficient between the coefficient of thermal expansion of the surface layer 114 and that of the partition wall 112 is preferably provided between the surface layer 114 and the partition wall 112. This can prevent cracks from occurring due to the difference in thermal expansion coefficients between the surface layer 114 and the partition wall 112, and improve thermal shock resistance. Although the composition of the stress relaxation layer is not particularly limited, for example, a low expansion glass layer, an alumina layer, a silica layer, or a ceria layer can be suitably used.

(3.ハニカム構造体の製造方法)
以下、ハニカム構造体の製造方法を説明する。
(3. Manufacturing method of honeycomb structure)
Hereinafter, a method for manufacturing a honeycomb structure will be explained.

まず、多孔質の隔壁を有し、隔壁によって複数のセルが区画形成されたハニカム構造体を作製する。例えば、コージェライトからなるハニカム構造体を作製する場合には、まず、坏土用材料としてコージェライト化原料を用意する。コージェライト化原料は、コージェライト結晶の理論組成となるように各成分を配合するため、シリカ源成分、マグネシア源成分、及びアルミナ源成分等を配合する。このうちシリカ源成分としては、石英、溶融シリカを用いることが好ましく、更に、このシリカ源成分の粒径を100~150μmとすることが好ましい。 First, a honeycomb structure having porous partition walls and having a plurality of cells defined by the partition walls is manufactured. For example, when producing a honeycomb structure made of cordierite, first, a raw material for forming cordierite is prepared as a clay material. The raw material for forming cordierite contains a silica source component, a magnesia source component, an alumina source component, and the like in order to blend each component so as to have a theoretical composition of cordierite crystal. Among these, it is preferable to use quartz or fused silica as the silica source component, and it is further preferable that the particle size of this silica source component is 100 to 150 μm.

マグネシア源成分としては、例えば、タルク、マグネサイト等を挙げることができる。これらの中でも、タルクが好ましい。タルクは、コージェライト化原料中37~43質量%含有させることが好ましい。タルクの粒径(平均粒子径)は、5~50μmであることが好ましく、10~40μmであることが更に好ましい。また、マグネシア(MgO)源成分は、不純物としてFe23、CaO、Na2O、K2O等を含有していてもよい。 Examples of magnesia source components include talc and magnesite. Among these, talc is preferred. Talc is preferably contained in an amount of 37 to 43% by mass in the cordierite forming raw material. The particle size (average particle size) of talc is preferably 5 to 50 μm, more preferably 10 to 40 μm. Moreover, the magnesia (MgO) source component may contain Fe 2 O 3 , CaO, Na 2 O, K 2 O, etc. as impurities.

アルミナ源成分としては、不純物が少ないという点で、酸化アルミニウム及び水酸化アルミニウムの少なくともいずれか一種を含有するものが好ましい。また、コージェライト化原料中、水酸化アルミニウムは10~30質量%含有させることが好ましく、酸化アルミニウムは0~20質量%含有させることが好ましい。 As the alumina source component, it is preferable to use one containing at least one of aluminum oxide and aluminum hydroxide, since it contains few impurities. Further, in the raw material for forming cordierite, aluminum hydroxide is preferably contained in an amount of 10 to 30% by mass, and aluminum oxide is preferably contained in an amount of 0 to 20% by mass.

次に、コージェライト化原料に添加する坏土用材料(添加剤)を用意する。添加剤として、少なくともバインダと造孔剤を用いる。そして、バインダと造孔剤以外には、分散剤や界面活性剤を使用することができる。 Next, a clay material (additive) to be added to the raw material for forming cordierite is prepared. At least a binder and a pore-forming agent are used as additives. In addition to the binder and the pore-forming agent, a dispersant and a surfactant can be used.

造孔剤としては、コージェライトの焼成温度以下において酸素と反応して酸化除去可能な物質、又は、コージェライトの焼成温度以下の温度に融点を有する低融点反応物質等を用いることができる。酸化除去可能な物質としては、例えば、樹脂(特に、粒子状の樹脂)、黒鉛(特に、粒子状の黒鉛)等を挙げることができる。低融点反応物質としては、鉄、銅、亜鉛、鉛、アルミニウム、及びニッケルからなる群より選択される少なくとも一種の金属、これらの金属を主成分とする合金(例えば、鉄の場合には炭素鋼や鋳鉄、ステンレス鋼)、又は、二種以上を主成分とする合金を用いることができる。これらの中でも、低融点反応物質は、粉粒状又は繊維状の鉄合金であることが好ましい。更に、その粒径又は繊維径(平均径)は10~200μmであることが好ましい。低融点反応物質の形状は、球状、巻菱形状、金平糖状等が挙げられ、これらの形状であると、細孔の形状をコントロールすることが容易となるため好ましい。 As the pore-forming agent, a substance that can be removed by oxidation by reacting with oxygen at a temperature below the firing temperature of cordierite, or a low melting point reactive substance having a melting point at a temperature below the firing temperature of cordierite, etc. can be used. Examples of substances that can be removed by oxidation include resins (especially particulate resins), graphite (particularly particulate graphites), and the like. As the low melting point reactant, at least one metal selected from the group consisting of iron, copper, zinc, lead, aluminum, and nickel, alloys containing these metals as main components (for example, in the case of iron, carbon steel or cast iron, stainless steel), or an alloy containing two or more of them as main components. Among these, the low melting point reactant is preferably a powdery or fibrous iron alloy. Furthermore, the particle size or fiber diameter (average diameter) is preferably 10 to 200 μm. Examples of the shape of the low melting point reactant include a spherical shape, a diamond-shaped shape, a confetti shape, and the like, and these shapes are preferable because the shape of the pores can be easily controlled.

バインダとしては、例えば、ヒドロキシプロピルメチルセルロース、メチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース、ポリビニルアルコール等を挙げることができる。また、分散剤としては、例えば、デキストリン、ポリアルコール等を挙げることができる。また、界面活性剤としては、例えば、脂肪酸石鹸を挙げることができる。なお、添加剤は、一種単独又は二種以上用いることができる。 Examples of the binder include hydroxypropylmethylcellulose, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, and polyvinyl alcohol. Furthermore, examples of the dispersant include dextrin, polyalcohol, and the like. Furthermore, examples of surfactants include fatty acid soaps. Note that the additives can be used alone or in combination of two or more.

次に、コージェライト化原料100質量部に対して、バインダを3~8質量部、造孔剤を3~40質量部、分散剤を0.1~2質量部、水を10~40質量部の割合で混合し、これら坏土用材料を混練し、坏土を調製する。 Next, to 100 parts by mass of the raw material for forming cordierite, 3 to 8 parts by mass of binder, 3 to 40 parts by mass of pore-forming agent, 0.1 to 2 parts by mass of dispersant, and 10 to 40 parts by mass of water. These clay materials are kneaded to prepare clay.

次に、調製した坏土を、押出成形法、射出成形法、プレス成形法等でハニカム形状に成形し、生のハニカム成形体を得る。連続成形が容易であり、例えばコージェライト結晶を配向させることができることから、押出成形法を採用することが好ましい。押出成形法は、真空土練機、ラム式押出成形機、2軸スクリュー式連続押出成形機等の装置を用いて行うことができる。 Next, the prepared clay is molded into a honeycomb shape by extrusion molding, injection molding, press molding, etc. to obtain a raw honeycomb molded body. It is preferable to employ an extrusion molding method because continuous molding is easy and, for example, cordierite crystals can be oriented. The extrusion molding method can be carried out using a device such as a vacuum clay kneader, a ram extruder, or a twin-screw continuous extruder.

次に、ハニカム成形体を乾燥させて所定の寸法に調整してハニカム乾燥体を得る。ハニカム成形体の乾燥は、熱風乾燥、マイクロ波乾燥、誘電乾燥、減圧乾燥、真空乾燥、凍結乾燥等で行うことができる。なお、全体を迅速且つ均一に乾燥することができることから、熱風乾燥と、マイクロ波乾燥又は誘電乾燥と、を組み合わせて乾燥を行うことが好ましい。 Next, the honeycomb molded body is dried and adjusted to predetermined dimensions to obtain a dried honeycomb body. The honeycomb formed body can be dried by hot air drying, microwave drying, dielectric drying, reduced pressure drying, vacuum drying, freeze drying, or the like. In addition, since the whole can be dried quickly and uniformly, it is preferable to perform drying by combining hot air drying and microwave drying or dielectric drying.

次に、目封止部の原料を用意する。目封止部の材料(目封止用スラリー)は、隔壁(ハニカム乾燥体)と同じ坏土用材料を用いてもよいし、異なる材料を用いてもよい。具体的には、セラミックス原料、界面活性剤、及び水を混合し、必要に応じて焼結助剤、造孔剤等を添加してスラリー状にし、ミキサー等を使用して混練することにより得ることができる。 Next, raw materials for the plugging portions are prepared. As the material for the plugging portions (slurry for plugging), the same clay material as that for the partition walls (dried honeycomb body) may be used, or a different material may be used. Specifically, it is obtained by mixing ceramic raw materials, surfactants, and water, adding sintering aids, pore-forming agents, etc. as necessary to form a slurry, and kneading using a mixer etc. be able to.

次に、ハニカム乾燥体の一方の端面のセル開口部の一部にマスクを施し、その端面を、目封止用スラリーが貯留された貯留容器中に浸漬して、マスクをしていないセルに目封止用スラリーを充填する。同様にして、ハニカム乾燥体の他方の端面のセル開口部の一部にマスクを施し、その端面を、目封止用スラリーが貯留された貯留容器中に浸漬して、マスクをしていないセルに目封止用スラリーを充填する。その後、乾燥させ、焼成することによって、目封止部を有するハニカム構造体を得る。上記乾燥の条件は、ハニカム成形体を乾燥させる条件と同様の条件を採用することができる。また、上記焼成の条件は、コージェライト化原料を用いた場合には、通常、大気雰囲気下、1410~1440℃の温度で3~15時間とすることができる。 Next, a part of the cell openings on one end face of the dried honeycomb body is masked, and the end face is immersed in a storage container in which plugging slurry is stored, and the unmasked cells are covered with a mask. Fill with plugging slurry. In the same manner, a part of the cell openings on the other end face of the dried honeycomb body is masked, and the end face is immersed in a storage container in which the plugging slurry is stored. Fill with plugging slurry. Thereafter, a honeycomb structure having plugged portions is obtained by drying and firing. The drying conditions may be the same as those for drying the honeycomb formed body. In addition, when a cordierite-forming raw material is used, the firing conditions can be generally set at a temperature of 1410 to 1440° C. for 3 to 15 hours in an air atmosphere.

また、得られたハニカム構造体は、その外周面に外周壁が形成された状態で作製される場合には、その外周面を研削し、外周壁を取り除いた状態としてもよい。このようにして外周壁を取り除いたハニカム構造体の外周に、後の工程にて、コーティング材を塗布して外周コーティングを形成する。また、外周面を研削する場合には、外周壁の一部を研削して取り除き、その部分に、コーティング材によって外周コーティングを形成してもよい。 Further, when the obtained honeycomb structure is manufactured with an outer peripheral wall formed on its outer peripheral surface, the outer peripheral surface may be ground and the outer peripheral wall removed. In a later step, a coating material is applied to the outer periphery of the honeycomb structure from which the outer peripheral wall has been removed to form an outer periphery coating. In addition, when grinding the outer circumferential surface, a part of the outer circumferential wall may be ground and removed, and an outer circumferential coating may be formed on that part using a coating material.

コーティング材を調製する場合には、例えば、2軸回転式の縦型ミキサーを用いて調製することができる。 When preparing a coating material, it can be prepared using, for example, a two-shaft rotary vertical mixer.

また、コーティング材には、コロイダルシリカ、有機バインダ、粘土等を更に含有させてもよい。なお、有機バインダは、0.05~0.5質量%用いることが好ましく、0.1~0.2質量%用いることが更に好ましい。また、粘土は、0.2~2.0質量%用いることが好ましく、0.4~0.8質量%用いることが更に好ましい。 Further, the coating material may further contain colloidal silica, organic binder, clay, etc. The organic binder is preferably used in an amount of 0.05 to 0.5% by mass, more preferably 0.1 to 0.2% by mass. Further, the clay is preferably used in an amount of 0.2 to 2.0% by mass, more preferably 0.4 to 0.8% by mass.

先に作製したハニカム構造体の外周面に、コーティング材を塗布し、塗布したコーティング材を乾燥させて、外周コーティングを形成する。このように構成することによって、乾燥・熱処理時の外周コーティングのクラックの発生を効果的に抑制することができる。 A coating material is applied to the outer circumferential surface of the honeycomb structure previously produced, and the applied coating material is dried to form an outer circumferential coating. With this configuration, it is possible to effectively suppress the occurrence of cracks in the outer peripheral coating during drying and heat treatment.

コーティング材の塗工方法としては、例えば、ハニカム構造体を回転台の上に載せて回転させ、コーティング材をブレード状の塗布ノズルから吐出させながらハニカム構造体の外周部に沿うように塗布ノズルを押し付けて塗布する方法を挙げることができる。このように構成することによって、コーティング材を均一な厚さで塗布することができる。また、形成した外周コーティングの表面粗さが小さくなり、外観に優れ、且つ熱衝撃によって破損し難い外周コーティングを形成することができる。 As a method for applying the coating material, for example, the honeycomb structure is placed on a rotary table and rotated, and the coating material is discharged from a blade-shaped application nozzle while applying the application nozzle along the outer periphery of the honeycomb structure. A method of applying by pressing can be mentioned. With this configuration, the coating material can be applied with a uniform thickness. Moreover, the surface roughness of the formed outer peripheral coating is reduced, and it is possible to form an outer peripheral coating that has an excellent appearance and is difficult to be damaged by thermal shock.

なお、ハニカム構造体の外周面が研削されて、外周壁が取り除かれたものの場合には、ハニカム構造体の外周面全体にコーティング材を塗布して外周コーティングを形成する。一方、ハニカム構造体の外周面に外周壁が存在する、或いは、一部の外周壁が取り除かれている場合には、部分的にコーティング材を塗布して外周コーティングを形成してもよいし、勿論、ハニカム構造体の外周面全域にコーティング材を塗布して外周コーティングを形成してもよい。 In addition, in the case where the outer circumferential surface of the honeycomb structure is ground and the outer circumferential wall is removed, a coating material is applied to the entire outer circumferential surface of the honeycomb structure to form an outer circumferential coating. On the other hand, if an outer peripheral wall exists on the outer peripheral surface of the honeycomb structure, or if a part of the outer peripheral wall is removed, a coating material may be applied partially to form an outer peripheral coating, Of course, the outer peripheral coating may be formed by applying the coating material to the entire outer peripheral surface of the honeycomb structure.

塗布したコーティング材(即ち、未乾燥の外周コーティング)を乾燥する方法については特に制限はないが、例えば、乾燥クラック防止の観点から、室温にて24時間以上保持することでコーティング材中の水分の25%以上を乾燥させた後、電気炉にて600℃で1時間以上保持することで水分及び有機物を除去する方法を好適に用いることができる。 There are no particular restrictions on the method of drying the applied coating material (i.e., the undried outer peripheral coating), but for example, from the perspective of preventing dry cracks, holding it at room temperature for 24 hours or more can remove moisture in the coating material. After drying 25% or more, it is possible to suitably use a method of removing water and organic substances by holding the product at 600° C. for 1 hour or more in an electric furnace.

また、ハニカム構造体のセルの開口部が予め封止されていない場合には、外周コーティングを形成した後に、セルの開口部に目封止を行ってもよい。 Furthermore, if the openings of the cells of the honeycomb structure are not sealed in advance, the openings of the cells may be plugged after forming the outer periphery coating.

また、得られたハニカム構造体は、その外周面にレーザーを照射することによって、コーティング材に含まれる炭化珪素粉末が発色するため、得られたハニカム構造体の外周コーティングに、レーザー光を照射して、製品情報等を印字(マーキング)してもよい。 In addition, the silicon carbide powder contained in the coating material develops color by irradiating the outer peripheral surface of the obtained honeycomb structure with laser light. It is also possible to print (mark) product information, etc.

レーザーによるマーキングの際に使用するレーザー光としては、例えば、炭酸ガス(CO2)レーザー、YAGレーザー、YVO4レーザーを好適例として挙げることができる。レーザー光を照射するレーザーの条件については、使用するレーザーの種類に応じて適宜選択することができるが、例えば、CO2レーザーを用いた場合には、出力15~25W、スキャンスピード400~600mm/sでマーキングすることが好ましい。このようにマーキングすることによって、照射部分が、黒色から緑色のような暗色を呈するように発色し、非照射部分との発色によるコントラストが極めて良好なものとなる。 Suitable examples of the laser beam used for laser marking include carbon dioxide (CO 2 ) laser, YAG laser, and YVO4 laser. The laser conditions for irradiating laser light can be selected appropriately depending on the type of laser used, but for example, when using a CO 2 laser, the output is 15 to 25 W, and the scanning speed is 400 to 600 mm/ It is preferable to mark with s. By marking in this way, the irradiated area develops a dark color such as black to green, and the contrast between the irradiated area and the non-irradiated area is extremely good.

ハニカム構造体に触媒を担持する場合には、上記レーザーによる印字を行った後でも、印字部分が劣化することがなく、触媒の担持後でも、上記印字を良好に判読することができる。なお、触媒の担持方法については特に制限はなく、従来のハニカム構造体の製造方法にて行われている触媒担持の方法に準じて行うことができる。 When a catalyst is supported on the honeycomb structure, the printed portion does not deteriorate even after the laser printing, and the printing can be read well even after the catalyst is supported. Note that there is no particular restriction on the method of supporting the catalyst, and it can be carried out in accordance with the method of supporting the catalyst carried out in the conventional manufacturing method of a honeycomb structure.

ハニカム構造体の隔壁の表面の少なくとも一部について、磁性体粒子を含み、かつ、通気性を有する表面層を形成する。また、前述のように、当該表面層は、隔壁の少なくとも片面を覆うことが好ましい。表面層を形成する方法として、主には、以下3つの方法がある。
・磁性体粒子と、金属又はガラスを主成分とする結合材とを含むスラリーをハニカム構造体のセル内に流し込んで塗膜を形成し、当該塗膜を金属の融点、又は、ガラスの軟化点以上の温度で加熱して表面層を形成する方法。
・磁性体粒子と、シリカ又はアルミナを主成分とする接着材料と、を含むスラリーをハニカム構造体のセル内に流し込んで塗膜を形成し、当該塗膜を加熱してシリカ又はアルミナを固化して表面層を形成する方法。
・磁性体粒子と、上記結合材又は上記接着材料とを含むガスをハニカム構造体のセル内に流し込む、あるいは磁性体粒子だけを含むガスをハニカム構造体のセル内に流し込んで塗膜を形成し、当該塗膜を加熱して表面層を形成する方法がある。
A surface layer containing magnetic particles and having air permeability is formed on at least a portion of the surface of the partition walls of the honeycomb structure. Moreover, as mentioned above, it is preferable that the surface layer covers at least one side of the partition wall. There are three main methods for forming the surface layer:
・A slurry containing magnetic particles and a binder mainly composed of metal or glass is poured into the cells of the honeycomb structure to form a coating film, and the coating film is heated to the melting point of the metal or the softening point of the glass. A method of forming a surface layer by heating at a temperature above.
・A slurry containing magnetic particles and an adhesive material mainly composed of silica or alumina is poured into the cells of a honeycomb structure to form a coating film, and the coating film is heated to solidify the silica or alumina. method to form a surface layer.
・A coating film is formed by flowing a gas containing magnetic particles and the above-mentioned binding material or the above-mentioned adhesive material into the cells of the honeycomb structure, or by flowing a gas containing only magnetic particles into the cells of the honeycomb structure. There is a method of heating the coating film to form a surface layer.

スラリーをハニカム構造体のセル内に流し込むには、例えば、スラリーをハニカム構造体のセル内に流通させる、又はスラリーをハニカム構造体のセル内に浸漬すればよい。ここで、金属又はガラスを主成分とする結合材を使用する場合は、製造時にハニカム基材の耐熱温度以下で一度溶融又は軟化させる必要があるので、結合材の融点又は軟化点の温度以上で塗膜を加熱することが好ましい。また、ハニカム構造体の使用環境においては、最高温度が約700℃に到達するため、この温度以上の融点又は軟化点を有する金属又はガラスを用いることがより好ましい。具体的な融点又は軟化点としては、例えば、800~1200℃である。一方、シリカ又はアルミナを主成分とする接着材料を用いる場合は、製造時に加熱乾燥によって接着材料が固化することができるものであることが好ましい。加熱乾燥によって上記接着材料が固化することができるものとしては、例えば、シリカまたはアルミナのコロイド分散体が挙げられ、シリカおよびアルミナを含むコロイド分散体であってもよい。
また、ハニカム構造体の使用環境における最高温度が約700℃に到達するため、この温度以上の耐熱温度を有するシリカ又はアルミナを用いることがより好ましい。スラリーをハニカム構造体のセル内に流し込んだ後、ハニカム構造体下流に吸引治具を取り付け、ハニカム構造体下流である他方の開口端部側より吸引し余剰水分を取り除き、塗膜を形成する。この塗膜を加熱処理する条件としては、温度800~1200℃、0.5~3時間で加熱することが好ましい。
アルミナやシリカを主成分とする接着材料を用いる場合においては、スラリーをセル内に流し込む工程はハニカム成形、乾燥体の段階で行っても良い。この場合は、スラリーをセル内に流し込んだ後、その表面層形成前のハニカム構造体を乾燥した後、ハニカム構造体の焼成工程において、磁性体粒子が接着材料に固定し表面層を形成する工程が同時に行われる。シリカ又はアルミナは、乾燥により固化する効果を発現することが好ましい。
また、上記金属やガラスを主成分とする結合材を添加する以外に、磁性体粒子に予め金属又はガラスを主成分とする結合材をコートさせておいてもよい。また、磁性体粒子と結合材を含む複合粒子を形成する工程を設けてもよい。
In order to pour the slurry into the cells of the honeycomb structure, for example, the slurry may be passed through the cells of the honeycomb structure, or the slurry may be immersed into the cells of the honeycomb structure. Here, when using a binding material whose main component is metal or glass, it is necessary to melt or soften it once at a temperature below the heat-resistant temperature of the honeycomb base material during manufacturing. Preferably, the coating is heated. Further, in the usage environment of the honeycomb structure, the maximum temperature reaches about 700° C., so it is more preferable to use a metal or glass having a melting point or softening point higher than this temperature. A specific melting point or softening point is, for example, 800 to 1200°C. On the other hand, when using an adhesive material containing silica or alumina as a main component, it is preferable that the adhesive material can be solidified by heating and drying during manufacturing. The adhesive material that can be solidified by heating and drying includes, for example, a colloidal dispersion of silica or alumina, and may also be a colloidal dispersion containing silica and alumina.
Further, since the maximum temperature in the usage environment of the honeycomb structure reaches about 700° C., it is more preferable to use silica or alumina that has a heat resistance temperature higher than this temperature. After pouring the slurry into the cells of the honeycomb structure, a suction jig is attached downstream of the honeycomb structure, and suction is performed from the other open end side downstream of the honeycomb structure to remove excess moisture and form a coating film. As the conditions for heat treating this coating film, it is preferable to heat it at a temperature of 800 to 1200° C. for 0.5 to 3 hours.
When using an adhesive material containing alumina or silica as a main component, the step of pouring the slurry into the cells may be performed during the honeycomb forming and drying stages. In this case, after pouring the slurry into the cells and drying the honeycomb structure before forming the surface layer, in the firing process of the honeycomb structure, the magnetic particles are fixed to the adhesive material to form the surface layer. are carried out simultaneously. Silica or alumina preferably exhibits the effect of solidifying upon drying.
Further, in addition to adding the above-mentioned binder mainly composed of metal or glass, the magnetic particles may be coated in advance with a binder mainly composed of metal or glass. Further, a step of forming composite particles containing magnetic particles and a binder may be provided.

スラリーは、例えば、磁性体粒子と、上記接着材料又は上記結合材と、有機バインダと、水又はアルコールと、を混合することで得ることができる。さらに、スラリーに対して、更に、油脂と、界面活性剤と、を加えて、混合し、エマルジョン化してもよい。また、スラリーには表面層の気孔率を制御するための造孔剤を混ぜておいても良い。造孔剤としては、例えば、粒子径0.5μm~10μmの樹脂粒子、デンプン粒子、カーボン粒子等を用いることができる。 The slurry can be obtained, for example, by mixing magnetic particles, the adhesive material or the binding material, an organic binder, and water or alcohol. Furthermore, an oil or fat and a surfactant may be further added to the slurry and mixed to form an emulsion. Further, a pore-forming agent may be mixed in the slurry in order to control the porosity of the surface layer. As the pore-forming agent, for example, resin particles, starch particles, carbon particles, etc. having a particle size of 0.5 μm to 10 μm can be used.

磁性体粒子と、及び上記結合材又は上記接着材料とを含むガスをハニカム構造体のセル内に流し込む方法として、例えば磁性体粒子を含むガスを0.005~0.4リットル/cm2でセル中に吹き込むことによって、浮遊状態の磁性体粒子を隔壁の表面に堆積させる。その後、例えば800~1200℃で0.5~3時間の条件で熱処理することにより、磁性体粒子を隔壁の表面に融着させて固定し、表面層を形成する。また、磁性体粒子だけを含むガスをハニカム構造体のセル内に流し込む場合は、例えば磁性体粒子を含むガスを0.005~0.4リットル/cm2でセル中に吹き込むことによって、浮遊状態の磁性体粒子を隔壁の表面に堆積させその後、1280~1330℃で0.5~3時間の条件で熱処理することにより、磁性体粒子を隔壁の表面に融着させて固定し、表面層を形成する。
結合材および接着材料を用いずに磁性体粒子のみをセル内に流し込む方法を含め、上述のスラリー又はガスをハニカム構造体のセル内に流し込む方法において、有機バインダをスラリー又はガスに混合させてもよい。有機バインダを加えることによって、加熱によって表面層を形成する工程よりも前の段階で、塗膜を仮固定することができる。有機バインダとしては、加熱により表面層を形成する工程の温度以下、すなわち800℃以下の酸化雰囲気で酸化除去されてしまう材料が好ましい。また、ハニカム構造体を製造する際の造孔剤として用いられるバインダと同様のバインダを用いることが好ましい。
As a method of flowing a gas containing magnetic particles and the above-mentioned binding material or above-mentioned adhesive material into the cells of a honeycomb structure, for example, a gas containing magnetic particles is poured into the cells at a rate of 0.005 to 0.4 liter/cm 2 . By blowing into the partition wall, suspended magnetic particles are deposited on the surface of the partition wall. Thereafter, the magnetic particles are fused and fixed to the surface of the partition wall by heat treatment at, for example, 800 to 1200° C. for 0.5 to 3 hours to form a surface layer. In addition, when flowing a gas containing only magnetic particles into the cells of a honeycomb structure, for example, by blowing the gas containing magnetic particles into the cells at a rate of 0.005 to 0.4 liters/cm 2 , a floating state can be created. The magnetic particles are deposited on the surface of the partition wall, and then heat treated at 1280 to 1330°C for 0.5 to 3 hours to fuse and fix the magnetic particles to the surface of the partition wall, forming a surface layer. Form.
In the above-mentioned method of pouring slurry or gas into the cells of a honeycomb structure, including the method of pouring only magnetic particles into the cells without using a binder or adhesive material, an organic binder may be mixed with the slurry or gas. good. By adding an organic binder, the coating film can be temporarily fixed at a stage before the step of forming a surface layer by heating. The organic binder is preferably a material that can be oxidized and removed in an oxidizing atmosphere at a temperature below the temperature of the step of forming the surface layer by heating, that is, below 800°C. Further, it is preferable to use a binder similar to the binder used as a pore-forming agent when manufacturing a honeycomb structure.

以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically explained based on Examples, but the present invention is not limited to these Examples.

(ハニカム構造体の作製)
[目封止ハニカム構造体の作製]
コージェライト化原料として、アルミナ、水酸化アルミニウム、カオリン、タルク、及びシリカを使用し、コージェライト化原料100質量部に、造孔剤を13質量部、分散媒を35質量部、有機バインダを6質量部、分散剤を0.5質量部、それぞれ添加し、混合、混練して坏土を調製した。
(Preparation of honeycomb structure)
[Production of plugged honeycomb structure]
Alumina, aluminum hydroxide, kaolin, talc, and silica are used as raw materials for cordierite formation, and 100 parts by mass of cordierite raw materials, 13 parts by mass of pore-forming agent, 35 parts by mass of dispersion medium, and 6 parts by mass of organic binder. Part by mass and 0.5 part by mass of a dispersant were added, mixed and kneaded to prepare clay.

分散媒として水を使用し、造孔剤としては平均粒子径10μmのコークスを使用し、有機バインダとしてはヒドロキシプロピルメチルセルロースを使用し、分散剤としてはエチレングリコールを使用した。次いで、所定の金型を用いて坏土を押出成形し、セル形状が四角形で、全体形状が円柱形(円筒形)のハニカム成形体を得た。 Water was used as a dispersion medium, coke with an average particle diameter of 10 μm was used as a pore-forming agent, hydroxypropylmethylcellulose was used as an organic binder, and ethylene glycol was used as a dispersant. Next, the clay was extruded using a predetermined mold to obtain a honeycomb molded body having square cell shapes and a cylindrical overall shape.

そして、ハニカム成形体をマイクロ波乾燥機で乾燥し、更に熱風乾燥機で完全に乾燥させた後、両端面を切断し、所定の寸法に整えてハニカム乾燥体を得た。次に、ハニカム乾燥体の一方の端面のセル開口部に、市松模様状に交互にマスクを施し、マスクを施した側の端部をコージェライト化原料を含有する目封止スラリーに浸漬し、市松模様状に交互に配列された目封止部を形成した。他方の端部については、一方の端部において目封止されたセルについてマスクを施し、上記一方の端部に目封止部を形成したのと同様の方法で目封止部を形成した。その後、熱風乾燥機で乾燥させ、更に、1410~1440℃で、5時間、焼成することによって、目封止ハニカム構造体(ハニカム担体)を得た。 Then, the honeycomb molded body was dried in a microwave dryer and further completely dried in a hot air dryer, and then both end faces were cut and adjusted to predetermined dimensions to obtain a dried honeycomb body. Next, the cell openings on one end surface of the dried honeycomb body are alternately masked in a checkerboard pattern, and the masked end is immersed in a plugging slurry containing a cordierite forming raw material, Plugged portions were formed that were alternately arranged in a checkerboard pattern. Regarding the other end, a mask was applied to the cells plugged at one end, and a plugged portion was formed in the same manner as in the method for forming the plugged portion at the one end. Thereafter, it was dried in a hot air dryer and further fired at 1410 to 1440°C for 5 hours to obtain a plugged honeycomb structure (honeycomb carrier).

(実施例1)
上記手順で作製したハニカム構造体について、その一方の端面側から、磁性体粒子、重量平均粒径が3μmの樹脂粒子、及び、結合材として重量平均粒径が5μmのシリカを主成分とするガラスを80:10:10の質量比で混合した粉末を調製した。この粉末を空気流に乗せてハニカム構造体に流通させ、その隔壁表面に堆積させ塗膜を形成した。この塗膜をガラスの軟化点以上の温度となるように、大気中950℃で1hr熱処理することにより、樹脂粒子を焼き飛ばすとともに、シリカを主成分とするガラスを溶融させて隔壁表面に粒子を固定し、表面層を形成した。
(Example 1)
Regarding the honeycomb structure produced by the above procedure, from one end surface side, magnetic particles, resin particles with a weight average particle size of 3 μm, and glass mainly composed of silica with a weight average particle size of 5 μm as a binder. A powder was prepared by mixing these at a mass ratio of 80:10:10. This powder was passed through the honeycomb structure in an air stream and deposited on the surface of the partition walls to form a coating film. This coating film is heat-treated in the air at 950°C for 1 hour to a temperature higher than the softening point of glass, thereby burning off the resin particles and melting the glass, which is mainly composed of silica, to coat the partition walls with particles. It was fixed to form a surface layer.

(実施例2)
長さL=10μm、L/d=1.00での針状の磁性体材料と、接着材料として乾燥により固化するシリカを主成分とする接着材料、有機バインダ、及び水を質量比85:10:5:500で混合してスラリーとした。このスラリーを霧吹きで霧化し、ハニカム構造体の端部から空気とともに吸引することにより、隔壁表面に堆積させ、乾燥し塗膜を形成した。その後、大気中600℃で1hrの熱処理で有機バインダを焼き飛ばし、大気中1000℃で1hr熱処理することによりシリカ又はアルミナを固化し、表面層を形成した。
(Example 2)
A needle-shaped magnetic material with a length L = 10 μm and L / d = 1.00, an adhesive material whose main component is silica that solidifies upon drying as an adhesive material, an organic binder, and water at a mass ratio of 85:10. :5:500 to form a slurry. This slurry was atomized by a sprayer and sucked together with air from the end of the honeycomb structure, thereby depositing it on the partition wall surface and drying to form a coating film. Thereafter, the organic binder was burned off by heat treatment at 600° C. for 1 hr in the air, and the silica or alumina was solidified by heat treatment at 1000° C. for 1 hr in the air to form a surface layer.

(実施例3)
長さL=20μm、L/d=4.00での針状の磁性体材料と、接着材料として乾燥により固化するシリカを主成分とする接着材料と、有機バインダと、水と、油脂と、界面活性剤とを質量比85:10:5:500:10:2で混合してエマルジョン化原料とした。このエマルジョン化原料を霧吹きで霧化し、ハニカム構造体の端部から空気とともに吸引することにより、隔壁表面に堆積させ、乾燥し塗膜を形成した。その後、大気中600℃で1hrの熱処理で有機バインダを焼き飛ばし、大気中1000℃で1hr熱処理することによりシリカ又はアルミナを固化し、表面層を形成した。
(Example 3)
A needle-shaped magnetic material with a length L = 20 μm and L / d = 4.00, an adhesive material whose main component is silica that solidifies when dried, an organic binder, water, oil and fat, A raw material for emulsification was prepared by mixing with a surfactant at a mass ratio of 85:10:5:500:10:2. This emulsion raw material was atomized by a sprayer, and was deposited on the partition wall surface by suctioning it together with air from the end of the honeycomb structure, and was dried to form a coating film. Thereafter, the organic binder was burned off by heat treatment at 600° C. for 1 hr in the air, and the silica or alumina was solidified by heat treatment at 1000° C. for 1 hr in the air to form a surface layer.

(実施例4)
ハニカム構造体を、入口端面である一方の開口端部を上にして、その上部にスラリーを貯めるスラリープールを取り付け、そこに、表面層形成用にスラリー(骨材として磁性体粒子、結合粒子としてSiO2、Al23、MgOを主成分とし、ガラス粉末)を入れた。そして、そのスラリーをハニカム構造体内にしみこませたのち、ハニカム構造体下流である他方の開口端部側より吸引し、余剰水分を取り除き、塗膜を形成した。その後、塗膜をガラス粉末の軟化点以上の温度として、950℃で乾燥、結合させて、表面層を形成させた。
(Example 4)
The honeycomb structure is placed with one open end, which is the inlet end face, facing upward, and a slurry pool for storing slurry is attached to the top of the honeycomb structure. The main components were SiO 2 , Al 2 O 3 and MgO, and glass powder) was added thereto. After the slurry was infiltrated into the honeycomb structure, it was sucked from the other open end side downstream of the honeycomb structure to remove excess moisture and form a coating film. Thereafter, the coating film was dried and bonded at 950° C. at a temperature higher than the softening point of the glass powder to form a surface layer.

(実施例5)
水95質量部に有機バインダであるカルボキシメチルセルロース0.5質量部を溶かし、その水溶液に、骨材粉末である最短径dが10μm、最長径Lが10μmの磁性体粒子(Cr18質量%のステンレス)2.5質量部、結合材としてSiO2、Al23、MgOを主成分とし、ガラス粉末のコロイド分散体(固形分40%)5質量部をこの順に加えて攪拌し、表面層形成用スラリーとした。そして、この表面層形成用スラリーに、ハニカム構造体の入口側を下にして出口目封止材深さ分だけ残して浸漬し、その後、引き上げ塗膜を形成した。これにより、入口開放セルの内表面にスラリーがディップコーティングされた。乾燥後、この塗膜をガラス粉末の軟化点以上の温度として、900℃で0.5時間熱処理することにより表面層を形成した。
(Example 5)
Dissolve 0.5 parts by mass of carboxymethyl cellulose, which is an organic binder, in 95 parts by mass of water, and add to the aqueous solution magnetic particles (stainless steel containing 18% Cr), which are aggregate powder and have a shortest diameter d of 10 μm and a longest diameter L of 10 μm. 2.5 parts by mass, mainly composed of SiO 2 , Al 2 O 3 and MgO as a binder, and 5 parts by mass of a colloidal dispersion of glass powder (solid content 40%) were added in this order and stirred to form a surface layer. It was made into a slurry. Then, the honeycomb structure was immersed in this slurry for forming a surface layer with the inlet side facing down, leaving a depth corresponding to the outlet plugging material, and then a pulled coating film was formed. This resulted in dip coating of the slurry on the inner surface of the inlet open cell. After drying, this coating film was heat-treated at 900° C. for 0.5 hours at a temperature higher than the softening point of the glass powder to form a surface layer.

(実施例6)
最長径L10μmの磁性体粒子を、空気、造孔剤、結合材としてのシリカを主成分とするガラス粉末と、共にハニカム構造体へ供給し、これらを隔壁上に堆積させ塗膜を形成した。このとき、表面層の気孔率や平均細孔直径は、造孔剤の粒度や粒度分布、添加量、供給空気量、などの条件を適宜設定することにより、制御することができる。ここでは、造孔剤として澱粉を用いた。更に、ハニカム構造体の上流領域や下流領域など、所定の領域の隔壁部に、アルコールや水、樹脂などを含ませておくことで、空気の透過抵抗を高めることにより、供給した表面層形成用原料や造孔剤の堆積領域を制御することができる。例えば、造孔剤の添加量を3質量部~45質量部としたり、造孔剤のメディアン径D50を0.7μm~8.0μmとしたり、造孔剤の粒度分布としてのシャープネス指標を0.4~1.9としたり、流体の流量を2000~8000L/minとしたりすることにより、表面層の気孔率、平均細孔直径などの値を変更した。塗膜をガラス粉末の軟化点以上の温度として大気中950℃で1hr熱処理することにより表面層を形成した。
(Example 6)
Magnetic particles with a longest diameter L of 10 μm were supplied to the honeycomb structure together with air, a pore-forming agent, and glass powder mainly composed of silica as a binder, and these were deposited on the partition walls to form a coating film. At this time, the porosity and average pore diameter of the surface layer can be controlled by appropriately setting conditions such as the particle size and particle size distribution of the pore-forming agent, the amount added, and the amount of air supplied. Here, starch was used as a pore-forming agent. Furthermore, by impregnating the partition walls in predetermined areas such as the upstream and downstream areas of the honeycomb structure with alcohol, water, resin, etc., the air permeation resistance is increased, and the supplied surface layer formation The deposition area of raw materials and pore-forming agents can be controlled. For example, the amount of the pore-forming agent added may be 3 parts by mass to 45 parts by mass, the median diameter D50 of the pore-forming agent may be 0.7 μm to 8.0 μm, or the sharpness index as the particle size distribution of the pore-forming agent may be 0.7 μm to 8.0 μm. The values of the porosity of the surface layer, average pore diameter, etc. were changed by adjusting the flow rate of the fluid to 2000 to 8000 L/min. A surface layer was formed by heat treating the coating film at 950° C. for 1 hour in the air at a temperature higher than the softening point of the glass powder.

(実施例7、8)
表1に示す、最長径L、最短径dを有する磁性体粒子を用いた以外は、実施例6と同様にしてハニカム構造体に表面層を形成した。
(Examples 7 and 8)
A surface layer was formed on a honeycomb structure in the same manner as in Example 6, except that magnetic particles having the longest diameter L and the shortest diameter d shown in Table 1 were used.

(実施例9)
表1に示す組成の磁性体粒子を用いた以外は、実施例1と同様にしてハニカム構造体に表面層を形成した。
(Example 9)
A surface layer was formed on a honeycomb structure in the same manner as in Example 1, except that magnetic particles having the composition shown in Table 1 were used.

(実施例10、11、12、13、14)
表1に示す、最長径L、最短径dの厚さの鱗片状磁性体粒子を用いた以外は、実施例6と同様にしてハニカム構造体に表面層を形成した。
(Examples 10, 11, 12, 13, 14)
A surface layer was formed on a honeycomb structure in the same manner as in Example 6, except that scale-like magnetic particles having a thickness of the longest diameter L and the shortest diameter d shown in Table 1 were used.

各実施例により得られるハニカム構造体の特性は表1に示す。 Table 1 shows the characteristics of the honeycomb structures obtained in each example.

Figure 0007423532000002
Figure 0007423532000002

実施例7のハニカム構造体を誘導加熱装置で、加熱試験を行った。投入電力は、4kWとし、誘導加熱周波数は30kHz、85kHz、350kHzで、ハニカム構造体の昇温性能を比較した。なお、誘導加熱周波数が30kHz、85kHzである場合は、ハニカム構造体の外周にコイルを6周分周回させ、350kHzである場合は、ハニカム構造体の外周にコイルを3周分周回させた。30kHz、85kHzで用いたコイルの無負荷のインダクタンスは2.5μHであり、350kHzで用いたコイルの無負荷のインダクタンスは1.0μHである。コイルに組み合わせたコンデンサは、30kHzの試験は10μFの容量、85kHzは1.3μFの容量、350kHzは0.2μFの容量のコンデンサを選んだ。トランスには、30kHzと85kHzの試験時は巻き数比が20:1を、350kHz試験には7:1を用いた。
誘導加熱周波数が30kHzでは十分な加熱速度が得られないが、350kHzでは90秒で500℃に加熱したことを確認した。図4に、当該加熱試験における各誘導加熱周波数30kHz、85kHz、350kHzにおける時間(秒)-温度(℃)の関係を表したグラフを示す。
A heating test was conducted on the honeycomb structure of Example 7 using an induction heating device. The input power was 4 kW, and the induction heating frequencies were 30 kHz, 85 kHz, and 350 kHz, and the temperature increase performance of the honeycomb structure was compared. Note that when the induction heating frequency was 30 kHz and 85 kHz, the coil was wound around the outer periphery of the honeycomb structure in 6 turns, and when it was 350 kHz, the coil was turned around the outer periphery of the honeycomb structure in 3 turns. The no-load inductance of the coil used at 30 kHz and 85 kHz is 2.5 μH, and the no-load inductance of the coil used at 350 kHz is 1.0 μH. As for the capacitor combined with the coil, a capacitor with a capacitance of 10 μF was selected for the 30 kHz test, a capacitor of 1.3 μF for the 85 kHz test, and a capacitor with a capacitance of 0.2 μF for the 350 kHz test. For the transformer, a turns ratio of 20:1 was used for the 30kHz and 85kHz tests, and a turns ratio of 7:1 was used for the 350kHz test.
Although a sufficient heating rate could not be obtained when the induction heating frequency was 30 kHz, it was confirmed that heating to 500° C. was achieved in 90 seconds at 350 kHz. FIG. 4 shows a graph showing the relationship between time (seconds) and temperature (° C.) at each induction heating frequency of 30 kHz, 85 kHz, and 350 kHz in the heating test.

実施例12のハニカム構造体を同様に誘導加熱装置で、加熱試験を行った。投入電力は、4kWとし、誘導加熱周波数は、350kHzで、ハニカム構造体の昇温性能を実施例7と比較した。実施例12の350kHzの誘導加熱試験でのコイル、コンデンサ、トランスの組合せは、実施例7と同じである。当該加熱試験における時間(秒)-温度(℃)の関係を表したグラフを図5に示す。
キュリー点が高い合金(Fe-49Co-2V合金)を用いることにより、触媒の酸化熱がなくても、ハニカム構造体を700℃まで加熱することができることを確認した。
The honeycomb structure of Example 12 was similarly subjected to a heating test using an induction heating device. The input power was 4 kW, the induction heating frequency was 350 kHz, and the temperature increase performance of the honeycomb structure was compared with Example 7. The combination of the coil, capacitor, and transformer in the 350 kHz induction heating test of Example 12 was the same as in Example 7. A graph showing the relationship between time (seconds) and temperature (°C) in the heating test is shown in FIG.
It was confirmed that by using an alloy with a high Curie point (Fe-49Co-2V alloy), the honeycomb structure could be heated to 700° C. without the oxidation heat of the catalyst.

いずれの実施例においても、図2に示される排気ガス浄化装置により加熱することができた。また、加熱の間には短絡が発生しなかった。 In any of the examples, heating could be performed using the exhaust gas purification device shown in FIG. Also, no short circuit occurred during heating.

上述の教示を踏まえ、当業者は、各実施形態に対して様々な変更を加えることができる。 Various modifications to the embodiments may be made by those skilled in the art in light of the above teachings.

1 ハニカム構造体
2 金属管
3 制御部
4、24 コイル配線
5 固定部材
6、26 排気ガス浄化装置
13 目封止部
20 排気システム
21 排気管
22 排気消音マフラー
25 保持マット
102 外周壁
104 第一端面
106 第二端面
108 第1セル
110 第2セル
112 隔壁
114 表面層
116 磁性体粒子
1 Honeycomb structure 2 Metal tube 3 Control section 4, 24 Coil wiring 5 Fixing member 6, 26 Exhaust gas purification device 13 Plugging section 20 Exhaust system 21 Exhaust pipe 22 Exhaust silencing muffler 25 Holding mat 102 Outer peripheral wall 104 First end surface 106 Second end face 108 First cell 110 Second cell 112 Partition wall 114 Surface layer 116 Magnetic particles

Claims (28)

流体の流路となり、流体の流入側の端面である流入端面から流体の流出側の端面である流出端面まで延びる複数のセルを区画形成する多孔質の隔壁と、
最外周に位置する外周壁と、
を有する柱状のハニカム構造体であって、
前記隔壁の表面の少なくとも一部に表面層を有し、前記表面層が、通気性を有し、かつ、
(1)磁性体粒子、及び、金属又はガラスを主成分とする結合材を含む、または、
(2)磁性体粒子、及び、シリカである接着材料を含む、
ことを特徴とするハニカム構造体。
a porous partition that forms a fluid flow path and defines a plurality of cells that extend from an inflow end face that is an end face on the fluid inflow side to an outflow end face that is the end face on the fluid outflow side;
an outer peripheral wall located at the outermost periphery;
A columnar honeycomb structure having
The partition wall has a surface layer on at least a part of the surface, and the surface layer has air permeability, and
(1) Contains magnetic particles and a binder whose main component is metal or glass, or
(2) containing magnetic particles and an adhesive material that is silica;
A honeycomb structure characterized by:
前記隔壁の少なくとも片面が前記表面層で覆われている請求項1に記載のハニカム構造体。 The honeycomb structure according to claim 1, wherein at least one side of the partition wall is covered with the surface layer. 前記磁性体粒子のキュリー温度が450℃を超える請求項1又は2に記載のハニカム構造体。 The honeycomb structure according to claim 1 or 2, wherein the Curie temperature of the magnetic particles exceeds 450°C. 前記表面層の気孔率が50%以上である請求項1~3のいずれかに記載のハニカム構造体。 The honeycomb structure according to any one of claims 1 to 3, wherein the surface layer has a porosity of 50% or more. 前記表面層の平均細孔直径が10μm以下である請求項1~4のいずれかに記載のハニカム構造体。 The honeycomb structure according to any one of claims 1 to 4, wherein the surface layer has an average pore diameter of 10 μm or less. 前記磁性体粒子の重量平均粒子径が20μm以下である請求項1~5のいずれかに記載のハニカム構造体。 The honeycomb structure according to any one of claims 1 to 5, wherein the weight average particle diameter of the magnetic particles is 20 μm or less. 前記表面層の厚みが10~80μmである請求項1~6のいずれかに記載のハニカム構造体。 The honeycomb structure according to any one of claims 1 to 6, wherein the surface layer has a thickness of 10 to 80 μm. 前記ハニカム構造体がセラミックス材料で形成される請求項1~7のいずれかに記載のハニカム構造体。 The honeycomb structure according to any one of claims 1 to 7, wherein the honeycomb structure is made of a ceramic material. 前記セラミックス材料がコージェライト、炭化珪素、チタン酸アルミニウム、窒化珪素、ムライト、アルミナからなる群から選択される少なくとも1つである請求項8に記載のハニカム構造体。 The honeycomb structure according to claim 8, wherein the ceramic material is at least one selected from the group consisting of cordierite, silicon carbide, aluminum titanate, silicon nitride, mullite, and alumina. 前記磁性体粒子の最短径dが0.1~5μmであり、
前記磁性体粒子の最長径をLμmとしたとき、L/d≧3である請求項1~9のいずれか1項に記載のハニカム構造体。
The shortest diameter d of the magnetic particles is 0.1 to 5 μm,
The honeycomb structure according to any one of claims 1 to 9, wherein L/d≧3, where Lμm is the longest diameter of the magnetic particles.
前記磁性体粒子が針状または鱗片状である請求項10に記載のハニカム構造体。 The honeycomb structure according to claim 10, wherein the magnetic particles are needle-shaped or scale-shaped. 前記表面層と前記隔壁との間に、前記表面層の熱膨張係数及び前記隔壁の熱膨張係数の間にある熱膨張係数を有する応力緩和層を備える請求項1~11のいずれかに記載のハニカム構造体。 12. A stress relaxation layer according to claim 1, further comprising a stress relaxation layer between the surface layer and the partition wall, the stress relaxation layer having a coefficient of thermal expansion between the coefficient of thermal expansion of the surface layer and the coefficient of thermal expansion of the partition wall. honeycomb structure. 前記セルは、前記流体の流入側が開口して前記流体の流出側の端面に目封止部を有する複数の第1セルと、前記流体の流出側が開口して前記流体の流入側の端面に目封止部を有する複数の第2セルとを含む請求項1~12のいずれかに記載のハニカム構造体。 The cells include a plurality of first cells that are open on the fluid inflow side and have plugging portions on the fluid outflow side end faces, and a plurality of first cells that are open on the fluid outflow side and have plugging portions on the fluid inflow side end faces. The honeycomb structure according to any one of claims 1 to 12, comprising a plurality of second cells having a sealing part. 流体の流路となり、流体の流入側の端面である流入端面から流体の流出側の端面である流出端面まで延びる複数のセルを区画形成する多孔質の隔壁と、
最外周に位置する外周壁と、
を有する柱状のハニカム構造体であって、
前記隔壁の表面の少なくとも一部に表面層を有し、前記表面層が、
(1)針状または鱗片状の磁性体粒子、及び、金属又はガラスを主成分とする結合材を含む、または、
(2)針状または鱗片状の磁性体粒子、及び、シリカである接着材料を含む、
ことを特徴とするハニカム構造体。
a porous partition that forms a fluid flow path and defines a plurality of cells that extend from an inflow end face that is an end face on the fluid inflow side to an outflow end face that is the end face on the fluid outflow side;
an outer peripheral wall located at the outermost periphery;
A columnar honeycomb structure having
The partition wall has a surface layer on at least a part of the surface, and the surface layer is
(1) Contains needle-like or scale-like magnetic particles and a binder whose main component is metal or glass, or
(2) Contains needle-like or scale-like magnetic particles and an adhesive material that is silica;
A honeycomb structure characterized by:
請求項1~14のいずれかに記載のハニカム構造体と、
前記ハニカム構造体の外周を螺旋状に周回するコイル配線と、
前記コイル配線の外側に設けられた、前記コイル配線を排ガス流路内に固定するための固定部材と、
を有する排気ガス浄化装置。
The honeycomb structure according to any one of claims 1 to 14,
a coil wiring spirally surrounding the outer periphery of the honeycomb structure;
a fixing member provided outside the coil wiring for fixing the coil wiring within the exhaust gas flow path;
An exhaust gas purification device with
排気消音マフラーと、
前記排気消音マフラー内に設けられた、請求項15に記載の排気ガス浄化装置と、
前記排気消音マフラー内に設けられた消音器と、
を備えた排気システム。
Exhaust silencing muffler,
The exhaust gas purification device according to claim 15, provided in the exhaust muffler,
a muffler provided in the exhaust muffler;
Exhaust system with.
流体の流路となり、流体の流入側の端面である流入端面から流体の流出側の端面である流出端面まで延びる複数のセルを区画形成する多孔質の隔壁と、
最外周に位置する外周壁と、
を有する柱状のハニカム構造体の製造方法であって、
前記隔壁の表面の少なくとも一部について、通気性を有する表面層であって、
(1)磁性体粒子、及び、金属又はガラスを主成分とする結合材を含む、または、
(2)磁性体粒子、及び、シリカである接着材料を含む、
前記表面層を形成する工程を含むことを特徴とするハニカム構造体の製造方法。
a porous partition that forms a fluid flow path and defines a plurality of cells that extend from an inflow end face that is an end face on the fluid inflow side to an outflow end face that is the end face on the fluid outflow side;
an outer peripheral wall located at the outermost periphery;
A method for manufacturing a columnar honeycomb structure, comprising:
A surface layer having air permeability for at least a portion of the surface of the partition wall,
(1) Contains magnetic particles and a binder whose main component is metal or glass, or
(2) containing magnetic particles and an adhesive material that is silica;
A method for manufacturing a honeycomb structure, comprising the step of forming the surface layer.
前記磁性体粒子を含み、かつ、通気性を有する表面層を形成する工程において、前記隔壁の少なくとも片面を前記表面層で覆う請求項17に記載のハニカム構造体の製造方法。 18. The method for manufacturing a honeycomb structure according to claim 17, wherein in the step of forming the surface layer containing the magnetic particles and having air permeability, at least one side of the partition wall is covered with the surface layer. 前記磁性体粒子を含み、かつ、通気性を有する表面層を形成する工程は、
磁性体粒子と、金属又はガラスを主成分とする結合材と、を含むスラリーを前記セル内に流し込み塗膜を形成するステップ、及び
前記塗膜を前記金属の融点、又は、前記ガラスの軟化点以上の温度で加熱して前記表面層を形成するステップ
を含む請求項17又は18に記載のハニカム構造体の製造方法。
The step of forming a surface layer containing the magnetic particles and having air permeability,
pouring a slurry containing magnetic particles and a binder mainly composed of metal or glass into the cell to form a coating film; and depositing the coating film at the melting point of the metal or the softening point of the glass. The method for manufacturing a honeycomb structure according to claim 17 or 18, comprising the step of forming the surface layer by heating at a temperature above.
前記磁性体粒子を含み、かつ、通気性を有する表面層を形成する工程は、
磁性体粒子と、シリカを主成分とする接着材料と、を含むスラリーを前記セル内に流し込み塗膜を形成するステップ、及び
前記塗膜を加熱して、前記シリカを固化して前記表面層を形成するステップ
を含む請求項17又は18に記載のハニカム構造体の製造方法。
The step of forming a surface layer containing the magnetic particles and having air permeability,
pouring a slurry containing magnetic particles and an adhesive material mainly composed of silica into the cells to form a coating film, and heating the coating film to solidify the silica and remove the surface layer. The method for manufacturing a honeycomb structure according to claim 17 or 18, comprising the step of forming.
前記磁性体粒子のキュリー温度が450℃を超える請求項17~20のいずれかに記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to any one of claims 17 to 20, wherein the Curie temperature of the magnetic particles exceeds 450°C. 前記表面層の気孔率が50%以上である請求項17~21のいずれかに記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structure according to any one of claims 17 to 21, wherein the surface layer has a porosity of 50% or more. 前記表面層の平均細孔直径が10μm以下である請求項17~22のいずれかに記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structure according to any one of claims 17 to 22, wherein the surface layer has an average pore diameter of 10 μm or less. 前記磁性体粒子の重量平均粒子径が20μm以下である請求項17~23のいずれかに記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structured body according to any one of claims 17 to 23, wherein the weight average particle diameter of the magnetic particles is 20 μm or less. 前記表面層の厚みが10~80μmである請求項17~24のいずれかに記載のハニカム構造体の製造方法。 The method for manufacturing a honeycomb structure according to any one of claims 17 to 24, wherein the surface layer has a thickness of 10 to 80 μm. 前記ハニカム構造体がセラミックス材料で形成されており、
前記セラミックス材料がコージェライト、炭化珪素、チタン酸アルミニウム、窒化珪素、ムライト、アルミナからなる群から選択される少なくとも1つである請求項25に記載のハニカム構造体の製造方法。
The honeycomb structure is formed of a ceramic material,
26. The method for manufacturing a honeycomb structured body according to claim 25, wherein the ceramic material is at least one selected from the group consisting of cordierite, silicon carbide, aluminum titanate, silicon nitride, mullite, and alumina.
前記磁性体粒子の最短径dが0.1~5μmであり、
前記磁性体粒子の最長径をLμmとしたとき、L/d≧3である請求項17~26のいずれかに記載のハニカム構造体の製造方法。
The shortest diameter d of the magnetic particles is 0.1 to 5 μm,
The method for manufacturing a honeycomb structure according to any one of claims 17 to 26, wherein L/d≧3, where Lμm is the longest diameter of the magnetic particles.
前記磁性体粒子が針状または鱗片状である請求項26に記載のハニカム構造体の製造方法。 27. The method for manufacturing a honeycomb structure according to claim 26, wherein the magnetic particles are needle-shaped or scale-shaped.
JP2020536318A 2018-08-10 2019-04-17 Honeycomb structure, exhaust gas purification device, exhaust system, and manufacturing method of honeycomb structure Active JP7423532B2 (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP2018151974 2018-08-10
JP2018151973 2018-08-10
JP2018151973 2018-08-10
JP2018151974 2018-08-10
JP2018230370 2018-12-07
JP2018230370 2018-12-07
JP2019022106 2019-02-08
JP2019022106 2019-02-08
PCT/JP2019/016520 WO2020031434A1 (en) 2018-08-10 2019-04-17 Honeycomb structural body, exhaust gas purification device, exhaust system, and method for producing honeycomb structural body

Publications (2)

Publication Number Publication Date
JPWO2020031434A1 JPWO2020031434A1 (en) 2021-09-24
JP7423532B2 true JP7423532B2 (en) 2024-01-29

Family

ID=69414688

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2020536318A Active JP7423532B2 (en) 2018-08-10 2019-04-17 Honeycomb structure, exhaust gas purification device, exhaust system, and manufacturing method of honeycomb structure

Country Status (5)

Country Link
US (1) US11614011B2 (en)
JP (1) JP7423532B2 (en)
CN (1) CN112512993A (en)
DE (1) DE112019004048T5 (en)
WO (1) WO2020031434A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA3137990A1 (en) * 2019-06-21 2020-12-24 Climeworks Ag Adsorber structure for gas separation processes
WO2021186792A1 (en) * 2020-03-19 2021-09-23 日本碍子株式会社 Honeycomb structure, exhaust gas purification catalyst, and exhaust gas purification system
JP7368614B2 (en) * 2020-05-14 2023-10-24 日本碍子株式会社 Honeycomb structure and exhaust gas purification device
EP4163008A4 (en) * 2020-06-09 2024-07-10 Proterial Ltd Adsorption member and method for manufacturing same
CN116322945A (en) * 2020-11-04 2023-06-23 日本碍子株式会社 Catalyst carrier and induction heating catalytic system
CN116528960A (en) 2020-12-02 2023-08-01 日本碍子株式会社 Honeycomb structure, exhaust gas purifying device, and method for manufacturing honeycomb structure
US20220389851A1 (en) * 2021-06-02 2022-12-08 Corning Incorporated Segmented honeycomb heater
WO2024072781A1 (en) * 2022-09-30 2024-04-04 Corning Incorporated Methods of making honeycomb bodies with tracer particles
CN117646896B (en) * 2024-01-29 2024-04-12 东北大学 Self-heat-exchanging device for catalytic reduction of pollutants, heat-exchanging ceramic balls and combustor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005247605A (en) 2004-03-02 2005-09-15 Ngk Insulators Ltd Porous ceramic body and method for manufacturing the same
WO2016021186A1 (en) 2014-08-07 2016-02-11 日本特殊陶業株式会社 Exhaust gas flow path member, exhaust gas purification device, temperature raising method therefor, and magnetic body for exhaust gas flow path member

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3991447B2 (en) * 1998-05-26 2007-10-17 トヨタ自動車株式会社 Induction heat purification device for internal combustion engine
US20030086839A1 (en) * 2001-10-31 2003-05-08 Rivin Eugeny I. Catalytic reactors
JP2005207331A (en) * 2004-01-23 2005-08-04 Hoei Kogyo Kk Exhaust muffler apparatus
JP2006057584A (en) * 2004-08-23 2006-03-02 Toyota Motor Corp Exhaust gas purifying catalyst
WO2008136232A1 (en) 2007-04-27 2008-11-13 Ngk Insulators, Ltd. Honeycomb filter
CN101827638B (en) * 2007-08-03 2016-07-13 埃尔西韦公司 Porous body and method
JP5261256B2 (en) 2009-03-30 2013-08-14 日本碍子株式会社 Energized heat generating honeycomb body and manufacturing method thereof
JP4920752B2 (en) 2010-01-05 2012-04-18 日本碍子株式会社 Honeycomb structure
JP5524696B2 (en) 2010-04-22 2014-06-18 日本碍子株式会社 Method for manufacturing plugged honeycomb structure
CN101879448B (en) * 2010-06-24 2012-05-23 天津大学 Ordered structure catalyst for hydrogenation of oxalic ester for preparing ethylene glycol and preparation method thereof
US10132221B2 (en) 2013-09-18 2018-11-20 Advanced Technology Emission Solutions Inc. Apparatus and method for gaseous emissions treatment with enhanced catalyst distribution
GB2520776A (en) * 2013-12-02 2015-06-03 Johnson Matthey Plc Wall-flow filter comprising catalytic washcoat
JP6608598B2 (en) * 2015-02-26 2019-11-20 Jfeスチール株式会社 Manufacturing method of honeycomb structure
JP6694301B2 (en) * 2016-03-23 2020-05-13 日本碍子株式会社 Joined body and method for manufacturing joined body
JP2017186220A (en) * 2016-03-30 2017-10-12 日本碍子株式会社 Transition metal oxide-containing cerium dioxide particle
MY197926A (en) * 2016-05-11 2023-07-25 Basf Corp Catalyst composition comprising magnetic material adapted for inductive heating
CN107270311A (en) * 2017-06-09 2017-10-20 南通斐腾新材料科技有限公司 A kind of portable catalysis burning bed
DE112019005955T5 (en) * 2018-11-30 2021-08-12 Ngk Insulators, Ltd. Honeycomb structure, emission control device and exhaust system

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005247605A (en) 2004-03-02 2005-09-15 Ngk Insulators Ltd Porous ceramic body and method for manufacturing the same
WO2016021186A1 (en) 2014-08-07 2016-02-11 日本特殊陶業株式会社 Exhaust gas flow path member, exhaust gas purification device, temperature raising method therefor, and magnetic body for exhaust gas flow path member

Also Published As

Publication number Publication date
WO2020031434A1 (en) 2020-02-13
US11614011B2 (en) 2023-03-28
US20210115825A1 (en) 2021-04-22
DE112019004048T5 (en) 2021-05-20
CN112512993A (en) 2021-03-16
JPWO2020031434A1 (en) 2021-09-24

Similar Documents

Publication Publication Date Title
JP7423532B2 (en) Honeycomb structure, exhaust gas purification device, exhaust system, and manufacturing method of honeycomb structure
JP4386830B2 (en) Honeycomb filter for exhaust gas purification
JP7122393B2 (en) Honeycomb structure, exhaust gas purification device and exhaust system
JP7229272B2 (en) Honeycomb structure and exhaust gas purification device
JP2007290951A (en) Honeycomb structural body and method of manufacturing honeycomb structural body
US20210388749A1 (en) Honeycomb structure and exhaust gas purifying device
JP7153788B2 (en) Honeycomb structure, exhaust gas purification device, and method for manufacturing honeycomb structure
US20220362704A1 (en) Honeycomb structure and exhaust gas purifying device
JP7313456B2 (en) Honeycomb structure and exhaust gas purification device
CN113557088B (en) Honeycomb structure and exhaust gas purifying device
US20220120204A1 (en) Honeycomb structure and exhaust gas purifying device
WO2021049075A1 (en) Honeycomb structure and exhaust gas purification device
US12121886B2 (en) Honeycomb structure and exhaust gas purifying device
JP7368614B2 (en) Honeycomb structure and exhaust gas purification device
JP7325473B2 (en) Porous honeycomb structure and manufacturing method thereof

Legal Events

Date Code Title Description
A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20201112

A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20210317

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20220315

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20220614

C60 Trial request (containing other claim documents, opposition documents)

Free format text: JAPANESE INTERMEDIATE CODE: C60

Effective date: 20220805

C22 Notice of designation (change) of administrative judge

Free format text: JAPANESE INTERMEDIATE CODE: C22

Effective date: 20221101

C22 Notice of designation (change) of administrative judge

Free format text: JAPANESE INTERMEDIATE CODE: C22

Effective date: 20230322

C22 Notice of designation (change) of administrative judge

Free format text: JAPANESE INTERMEDIATE CODE: C22

Effective date: 20230404

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20231011

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20240117

R150 Certificate of patent or registration of utility model

Ref document number: 7423532

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150